EP0449015B1 - Difluoromethyl compounds and liquid criystal medium - Google Patents

Difluoromethyl compounds and liquid criystal medium Download PDF

Info

Publication number
EP0449015B1
EP0449015B1 EP91103627A EP91103627A EP0449015B1 EP 0449015 B1 EP0449015 B1 EP 0449015B1 EP 91103627 A EP91103627 A EP 91103627A EP 91103627 A EP91103627 A EP 91103627A EP 0449015 B1 EP0449015 B1 EP 0449015B1
Authority
EP
European Patent Office
Prior art keywords
trans
compounds
cyclohexyl
formula
propylcyclohexyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91103627A
Other languages
German (de)
French (fr)
Other versions
EP0449015A2 (en
EP0449015A3 (en
Inventor
Ekkehard Dr. Bartmann
Dieter Dr. Dorsch
Eike Dr. Poetsch
Reinhard Dr. Hittich
Bernhard Dr. Wacore-Tamagawagakuen Rieger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP0449015A2 publication Critical patent/EP0449015A2/en
Publication of EP0449015A3 publication Critical patent/EP0449015A3/en
Application granted granted Critical
Publication of EP0449015B1 publication Critical patent/EP0449015B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3048—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458—Uncondensed pyrimidines
    • C09K19/3469—Pyrimidine with a specific end-group other than alkyl, alkoxy or -C*-

Definitions

  • the invention further relates to the use of these Compounds as components of liquid crystalline media as well as liquid crystal and electro-optical display, which the Contain liquid-crystalline media according to the invention.
  • the compounds of formula I can be used as components liquid crystalline media are used, in particular for displays based on the principle of the twisted cell, the Guest-host effect, the effect of deformation erect Phases or the effect of dynamic scattering.
  • the invention was based, new stable task to find liquid-crystalline or mesogenic compounds, which are suitable as components of liquid-crystalline media and in particular at the same time a comparatively small one Have viscosity and a relatively high dielectric Anisotropy.
  • Liquid crystals of the following formulas: are already known from DE 39 09 802.
  • the compounds of formula I have a wide range of uses. Depending on the choice of substituents these compounds can serve as base materials from which liquid-crystalline media for the most part are composed; but connections of the Formula I liquid crystalline base materials from others Classes of compound can be added, for example the dielectric and / or optical anisotropy of such To influence the dielectric and / or its threshold voltage and / or optimize its viscosity.
  • the compounds of the formula I are colorless in the pure state and form liquid crystalline mesophases in one for the electro-optical use conveniently located temperature range. They are stable chemically, thermally and against light.
  • the invention thus relates to the compounds of Formula I and the use of these compounds as Components of liquid crystalline media.
  • Subject of Invention are also liquid crystalline media with a Content of at least one compound of the formula I and Liquid crystal display elements, especially electro-optical ones Display elements that contain such media.
  • Cyc is a 1,4-cyclohexylene radical
  • Che is 1,4-cyclohexenylene
  • dio is 1,3-dioxane-2,5-diyl
  • Dit 1,3-dithiane-2,5-diyl
  • Phe one 1,4-phenylene
  • Pyr a Pyrimidine-2,5-diyl residue
  • Bi a bicyclo (2,2,2) octylene residue.
  • the compounds of the formula I accordingly comprise the preferred compounds of the sub-formulas Ia, Ib and Ic
  • sub-formula Ic are particularly preferred.
  • R is preferably alkyl, furthermore alkoxy.
  • a 1 is preferably Phe, Cyc, Che, Pyr or Dio.
  • the compounds of the formula I preferably contain no more than one of the radicals Bi, Pyd, Pyr, Dio or Dit.
  • a 1 is 1,4-phenylene which is mono- or disubstituted by F or monosubstituted by CN.
  • a 1 is 1,4-phenylene which is mono- or disubstituted by F or monosubstituted by CN.
  • Z 1 preferably denotes a single bond, -CO-O-, -O-CO- and -CH 2 CH 2 -, in the second place preferably -CH 2 O- and -OCH 2 -.
  • R is an alkyl radical and / or an alkoxy radical, it can be straight or branched. Preferably it is straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly preferably means ethyl, propyl, butyl, pentyl, Hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or Heptoxy, also methyl, octyl, nonyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, Nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
  • R is an alkyl radical in which one CH 2 group has been replaced by -O- and one has been replaced by -CO-, these are preferably adjacent. Thus, these contain an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. These are preferably straight-chain and have 2 to 6 carbon atoms.
  • acryloyloxymethyl 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxy butyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxoyloxoyloxydylmethyl, methacryloyloxoyloxydoxyl, methacryloyloxydoxyl, methacrylate - methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl, 9-methacryloyloxynonyl.
  • Branched groups of this type usually do not contain more than a chain branch.
  • R represents an alkyl radical in which two or more CH 2 groups have been replaced by -O- and / or -CO-O-, this can be straight-chain or branched. It is preferably branched and has 3 to 12 carbon atoms. Accordingly, it means especially bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, Bis (methoxycarbonyl) methyl, 2,2-bis (methoxycarbonyl) ethyl, 3,3-bis (methoxycarbonyl) propyl, 4,4-bis (methoxycarbon
  • Formula I includes both the racemates of these compounds also the optical antipodes and their mixtures.
  • the 1,4-cyclohexenylene group preferably has the following structures:
  • the compounds of the formula I can be prepared, for example, by reacting corresponding aldehydes (which in turn can be obtained from corresponding, known nitriles by routine methods) with SF 4 .
  • starting materials can also be formed in situ be such that you can not from the reaction mixture isolated, but immediately continue to the connections of the Formula I implements.
  • acid halides are particularly suitable, especially those Chlorides and bromides, furthermore the anhydrides, e.g. also mixed anhydrides, azides or esters, especially alkyl esters with 1-4 C atoms in the alkyl group.
  • the esterification is advantageous in the presence of an inert Solvent carried out.
  • Ethers such as Diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as Acetone, butanone or cyclohexanone, Amides such as DMF or phosphoric acid hexamethyl triamide, Hydrocarbons such as Benzene, toluene or xylene, Halogenated hydrocarbons such as Carbon tetrachloride, Dichloromethane or tetrachlorethylene and sulfoxides such as e.g. Dimethyl sulfoxide or sulfolane.
  • Ethers of the formula I can be obtained by etherification of corresponding hydroxy compounds, preferably corresponding phenols, the hydroxy compound expediently first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 corresponding alkali metal alcoholate or alkali metal phenolate is converted.
  • Dioxane derivatives or dithiane derivatives of the formula I are expediently by reaction of an appropriate aldehyde (or one of its reactive derivatives) with one corresponding 1,3-diol (or one of its reactive Derivatives) or a corresponding 1,3-dithiol, preferably in the presence of an inert solvent such as e.g. Benzene or toluene and / or a catalyst e.g. a strong acid such as sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between about 20 ° and about 150 °, preferably between 80 ° and 120 °.
  • an inert solvent such as e.g. Benzene or toluene and / or a catalyst e.g. a strong acid such as sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between about 20 ° and about 150 °, preferably between 80 °
  • the aldehydes and 1,3-diols or 1,3-dithiols mentioned and some of their reactive derivatives are known to: Part of it can be done without difficulty using standard procedures of organic chemistry from compounds known from the literature getting produced.
  • the aldehydes are through Oxidation of appropriate alcohols or by reduction of Nitriles or corresponding carboxylic acids or their derivatives, the diols by reducing the corresponding diesters and the dithiols by reacting appropriate dihalides with NaSH available.
  • the compounds of the formula II can be prepared, for example, according to the following synthesis schemes:
  • the starting materials are either known or can be found in Analogy to known compounds.
  • an aryl halide is reacted with an olefin in the presence of a tertiary amine and a palladium catalyst (cf. RF Heck, Acc. Chem. Res. 12 (1979) 146).
  • Suitable aryl halides are, for example, chlorides, bromides and iodides, in particular bromides and iodides.
  • the tertiary amines required for the coupling reaction to succeed, such as triethylamine, are also suitable as solvents.
  • Suitable palladium catalysts are, for example, its salts, in particular Pd (II) acetate, with organic phosphorus (III) compounds such as, for example, triarylphosphines.
  • suitable solvents are nitriles such as acetonitrile or hydrocarbons such as benzene or toluene.
  • the aryl halides and olefins used as starting materials are commercially available in many cases or can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.
  • stilbene derivatives can be produced, for example.
  • the stilbenes can also be produced by reacting a 4-substituted benzaldehyde with a corresponding phosphorylide according to Wittig.
  • tolanes of the formula I can also be prepared by using monosubstituted acetylene instead of the olefin (Synthesis 627 (1980) or Tetrahedron Lett. 27 , 1171 (1986)).
  • Aryl halides can also be used to couple aromatics be implemented with aryl zinc compounds.
  • a catalyst such as e.g. of a palladium (O) complex in inert solvents such as Hydrocarbons at high temperatures, e.g. in boiling Xylene, carried out under protective gas.
  • Tolanes of the formula I can also be prepared via the Fritsch-Buttenberg-Wiechell rearrangement (Ann. 279 , 319, 332, 1984), in which 1,1-diaryl-2-halogenethylenes are rearranged to diarylacetylenes in the presence of strong bases.
  • Tolanes of formula I can also be prepared by the corresponding style level is brominated and then subject to dehydrohalogenation. You can do that well-known, not mentioned variants of this Apply implementation.
  • Ethers of the formula I can be obtained by etherification of corresponding hydroxy compounds, preferably corresponding phenols, the hydroxy compound expediently first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 corresponding alkali metal alcoholate or alkali metal phenolate is converted.
  • the containing compounds can be chlorinated using PCl 5 and convert the subsequent HCl elimination into the acetylene using a base.
  • the transformation of the -CH CH- bridged substances, which can be produced via Heck coupling or Wittig reaction, is accomplished in a conventional manner, for example by means of bromination and double HBr elimination.
  • the carboxylate group is introduced in analogy to the introduction of the CH 2 CH 2 group (cf. compound 7, formula scheme below) using CO 2 .
  • the intermediately formed acids can be esterified with the corresponding phenols, which can be prepared from 1 according to synthesis step ba.
  • the compound 8 can be according to d) to 12 and analogous to e) 13 implement.
  • 12 is by means of vinyl bromide according to bc) and 13 converted to 14 using divinyl zinc according to c).
  • 15 can obtained from 12 and 1 by means of cross coupling according to h) or from 13 and 3 by cross coupling.
  • the CH CH grouping can be converted into the CH 2 -CH 2 or -C ⁇ C grouping.
  • the liquid-crystalline media according to the invention contain preferably in addition to one or more of the invention Compounds as further components 2 to 40, in particular 4 to 30 components. Very particularly preferably included these media in addition to one or more of the invention Connections 7 to 25 components.
  • These other ingredients are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular Substances from the classes of azoxybenzenes, Benzylidenanilines, biphenyls, terphenyls, phenyl or Cyclohexylbenzoate, cyclohexane-carboxylic acid phenyl or cyclohexyl ester, phenyl or cyclohexyl ester of cyclohexylbenzoic acid, Phenyl or cyclohexyl ester of cyclohexylcyclohexane carboxylic acid, Cyclohexylphenyl ester of Benzoic acid, cyclo
  • L and E mean the same or can be different, each independently a bivalent residue from the from -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well whose mirror images formed group, whereby Phe unsubstituted or fluorine-substituted 1,4-phenylene, Cyc trans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr Pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio 1,3-dioxane-2,5-diyl and G 2- (trans-1,4-cyclohexyl) ethyl, pyrimidine-2,5-diyl, Pyridine-2,5-diyl
  • One of the radicals L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention contain one or more Components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein L and E are selected from the group Cyc, Phe and Pyr and simultaneously one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein one of the radicals L and E is selected from selected from the group Cyc, Phe and Pyr and the other residue is from the group -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein the residues L and E are selected from the Group -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc
  • R ′′ is -CN, -CF 3 , F, Cl or -NCS; R has the meaning given for the compounds of the partial formulas 1a to 5a and is preferably alkyl or alkenyl.
  • R has the meaning given for the compounds of the partial formulas 1a to 5a and is preferably alkyl or alkenyl.
  • R has the meaning given for the compounds of the partial formulas 1a to 5a and is preferably alkyl or alkenyl.
  • other variants of the proposed substituents in the compounds of the formulas 1, 2, 3, 4 and 5 are also common. Many such substances or mixtures thereof are commercially available. All of these substances can be obtained by methods known from the literature
  • the media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of the invention Links. Media containing are also preferred more than 40%, in particular 45 to 90%, of the invention Links.
  • the media preferably contain three, four or five compounds according to the invention.
  • the media according to the invention are produced in yourself in the usual way. Usually the components dissolved in one another, expediently at elevated temperature.
  • suitable additives the invention can be modified so that it has been used in all known types of liquid crystal display elements can be used.
  • Such additives are known to the person skilled in the art known and described in detail in the literature (H. Kelker / R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980).
  • pleochroic Dyes for the production of colored guest-host systems or Substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic Phases are added.
  • 200 g of sulfuric tetrafluoride are condensed into an 800 ml Hastelloy autoclave which contains a mixture of 48 g of p- (trans-4-n-propylcyclohexyl) benzaldehyde and 0.1 g of potassium fluoride with cooling using an acetone / dry ice mixture .
  • the autoclave is then heated to 150 ° for 120 h. After cooling to approx. 30 °, the gaseous content of the autoclave is drained into wash bottles with sodium hydroxide solution.
  • Another 5 g of potassium fluoride, then 50 ml of pentane, then 10 g of sodium hydrogen carbonate and finally 100 ml of water are added to the residue (with stirring).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)
  • Pyridine Compounds (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Description

Die Erfindung betrifft neue Difluormethylverbindungen der Formel I,

Figure 00010001
worin

R
einen unsubstituierten oder einen mindestens einfach durch Halogen substituierten Alkyl-oder Alkenylrest mit 1 bis 15 C-Atomen, wobei in diesen Resten auch eine oder mehrere CH2-Gruppen jeweils unabhängig voneinander durch -O-, -S-,
Figure 00010002
-CO-, -CO-O-, -O-CO-oder -O-CO-O- so ersetzt sein können, daß O-Atome nicht direkt miteinander verknüpft sind,
A1 und A2
jeweils unabhängig voneinander einen
  • (a) trans-1,4-Cyclohexylenrest, worin auch eine oder mehrere nicht benachbarte CH2-Gruppen durch -O- und/oder -S- ersetzt sein können,
  • (b) 1,4-Phenylenrest, worin auch eine oder zwei CH-Gruppen durch N ersetzt sein können,
  • (c) Rest aus der Gruppe 1,4-Cyclohexenylen, 1,4-Bicyclo(2,2,2)-octylen, Piperidin-1,4-diyl, Naphthalin-2,6-diyl, Decahydronaphthalin-2,6-diyl und 1,2,3,4-Tetrahydronaphthalin-2,6-diyl,
    •
    wobei die Reste (a) und (b) mit CN oder 1-2 Fluor substituiert sein können,
    L1 und L2
    jeweils unabhängig voneinander H oder F,
    Z1
    -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH2CH2-, -CH=CH-, -C≡C- oder eine Einfachbindung und
    m
    0, 1, 2 oder 3 bedeutet,
    mit der Maßgabe für den Vertragsstaat DE, daß L1 und/oder L2 F bedeuten.The invention relates to new difluoromethyl compounds of the formula I,
    Figure 00010001
    wherein
    R
    an unsubstituted or an at least mono-substituted alkyl or alkenyl radical having 1 to 15 carbon atoms, one or more CH 2 groups in these radicals also being each independently of one another by -O-, -S-,
    Figure 00010002
    -CO-, -CO-O-, -O-CO-or -O-CO-O- can be replaced so that O atoms are not directly linked to each other,
    A 1 and A 2
    one each independently
  • (a) trans-1,4-cyclohexylene radical, in which one or more non-adjacent CH 2 groups can also be replaced by -O- and / or -S-,
  • (b) 1,4-phenylene radical, in which one or two CH groups can also be replaced by N,
  • (c) radical from the group 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) -octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6- diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
    • where the residues (a) and (b) can be substituted by CN or 1-2 fluorine,
    L 1 and L 2
    each independently of one another H or F,
    Z 1
    -CO-O-, -O-CO-, -CH 2 O-, -OCH 2 -, -CH 2 CH 2 -, -CH = CH-, -C≡C- or a single bond and
    m
    0, 1, 2 or 3 means
    with the proviso for the contracting state DE that L 1 and / or L 2 F.

    Die Erfindung betrifft weiterhin die Verwendung dieser Verbindungen als Komponenten flüssigkristalliner Medien sowie Flüssigkristall- und elektrooptische Anzeige, die die erfindungsgemäßen flüssigkristallinen Medien enthalten.The invention further relates to the use of these Compounds as components of liquid crystalline media as well as liquid crystal and electro-optical display, which the Contain liquid-crystalline media according to the invention.

    Die Verbindungen der Formel I können als Komponenten flüssigkristalliner Medien verwendet werden, insbesondere für Displays, die auf dem Prinzip der verdrillten Zelle, dem Guest-Host-Effekt, dem Effekt der Deformation aufgerichteter Phasen oder dem Effekt der dynamischen Streuung beruhen.The compounds of formula I can be used as components liquid crystalline media are used, in particular for displays based on the principle of the twisted cell, the Guest-host effect, the effect of deformation erect Phases or the effect of dynamic scattering.

    Der Erfindung lag die Aufgabe zugrunde, neue stabile flüssigkristalline oder mesogene Verbindungen aufzufinden, die als Komponenten flüssigkristalliner Medien geeignet sind und insbesondere gleichzeitig eine vergleichsweise geringe Viskosität besitzen sowie eine relativ hohe dielektrische Anisotropie.The invention was based, new stable task to find liquid-crystalline or mesogenic compounds, which are suitable as components of liquid-crystalline media and in particular at the same time a comparatively small one Have viscosity and a relatively high dielectric Anisotropy.

    Es wurde nun gefunden, daß Verbindungen der Formel I als Komponenten flüssigkristalliner Medien vorzüglich geeignet sind. Insbesondere verfügen sie über vergleichsweise niedere Viskositäten. Mit ihrer Hilfe lassen sich stabile flüssigkristalline Medien mit breitem Mesophasenbereich und vorteilhaften Werten für die optische und dielektrische Anisotropie erhalten.It has now been found that compounds of the formula I as Components of liquid crystalline media are particularly suitable are. In particular, they have comparatively low levels Viscosities. With their help stable liquid crystalline Media with a wide mesophase range and advantageous Optical and dielectric anisotropy values receive.

    Flüssigkristalle der folgenden Formeln:

    Figure 00040001
    sind bereits aus DE 39 09 802 bekannt.Liquid crystals of the following formulas:
    Figure 00040001
    are already known from DE 39 09 802.

    Im Hinblick auf die verschiedensten Einsatzbereiche derartiger Verbindungen war es jedoch wünschenswert, weitere Verbindungen zur Verfügung zu haben, die auf die jeweiligen Anwendungen genau maßgeschneiderte Eigenschaften aufweisen.With regard to the most diverse areas of application Connections, however, it was desirable to add more connections to have available that on each Applications have precisely tailored properties.

    Mit der Bereitstellung von Verbindungen der Formel I wird außerdem ganz allgemein die Palette der flüssigkristallinen Substanzen, die sich unter verschiedenen anwendungstechnischen Gesichtspunkten zur Herstellung flüssigkristalliner Gemische eignen, erheblich verbreitert. With the provision of compounds of formula I will also generally the range of liquid crystalline Substances that can be found under different application technology Aspects for the production of liquid crystalline Mixtures are suitable, considerably widened.

    Die Verbindungen der Formel I besitzen einen breiten Anwendungsbereich. In Abhängigkeit von der Auswahl der Substituenten können diese Verbindungen als Basismaterialien dienen, aus denen flüssigkristalline Medien zum überwiegenden Teil zusammengesetzt sind; es können aber auch Verbindungen der Formel I flüssigkristallinen Basismaterialien aus anderen Verbindungsklassen zugesetzt werden, um beispielsweise die dielektrische und/oder optische Anisotropie eines solchen Dielektrikums zu beeinflussen und/oder um dessen Schwellenspannung und/ oder dessen Viskosität zu optimieren.The compounds of formula I have a wide range of uses. Depending on the choice of substituents these compounds can serve as base materials from which liquid-crystalline media for the most part are composed; but connections of the Formula I liquid crystalline base materials from others Classes of compound can be added, for example the dielectric and / or optical anisotropy of such To influence the dielectric and / or its threshold voltage and / or optimize its viscosity.

    Die Verbindungen der Formel I sind in reinem Zustand farblos und bilden flüssigkristalline Mesophasen in einem für die elektrooptische Verwendung günstig gelegenen Temperaturbereich. Chemisch, thermisch und gegen Licht sind sie stabil.The compounds of the formula I are colorless in the pure state and form liquid crystalline mesophases in one for the electro-optical use conveniently located temperature range. They are stable chemically, thermally and against light.

    Gegenstand der Erfindung sind somit die Verbindungen der Formel I sowie die Verwendung dieser Verbindungen als Komponenten flüssigkristalliner Medien. Gegenstand der Erfindung sind ferner flüssigkristalline Medien mit einem Gehalt an mindestens einer Verbindung der Formel I sowie Flüssigkristallanzeigeelemente, insbesondere elektroopische Anzeigeelemente, die derartige Medien enthalten.The invention thus relates to the compounds of Formula I and the use of these compounds as Components of liquid crystalline media. Subject of Invention are also liquid crystalline media with a Content of at least one compound of the formula I and Liquid crystal display elements, especially electro-optical ones Display elements that contain such media.

    Der Einfachheit halber bedeuten im folgenden Cyc einen 1,4-Cyclohexylenrest, Che einen 1,4-Cyclohexenylenrest, Dio einen 1,3-Dioxan-2,5-diylrest, Dit einen 1,3-Dithian-2,5-diylrest, Phe einen 1,4-Phenylenrest, Pyd einen Pyridin-2,5-diylrest, Pyr einen Pyrimidin-2,5-diylrest und Bi einen Bicyclo(2,2,2)-octylenrest.For the sake of simplicity, mean below Cyc is a 1,4-cyclohexylene radical, Che is 1,4-cyclohexenylene, dio is 1,3-dioxane-2,5-diyl, Dit 1,3-dithiane-2,5-diyl, Phe one 1,4-phenylene, Pyd a pyridine-2,5-diyl residue, Pyr a Pyrimidine-2,5-diyl residue and Bi a bicyclo (2,2,2) octylene residue.

    Die Verbindungen der Formel I umfassen dementsprechend die bevorzugten Verbindungen der Teilformeln Ia, Ib und Ic

    Figure 00060001
    The compounds of the formula I accordingly comprise the preferred compounds of the sub-formulas Ia, Ib and Ic
    Figure 00060001

    Darunter sind besonders diejenigen der Teilformel Ic bevorzugt.Among them, those of sub-formula Ic are particularly preferred.

    R bedeutet vorzugsweise Alkyl, ferner Alkoxy. A1 bedeutet bevorzugt Phe, Cyc, Che, Pyr oder Dio. Bevorzugt enthalten die Verbindungen der Formel I nicht mehr als einen der Reste Bi, Pyd, Pyr, Dio oder Dit. R is preferably alkyl, furthermore alkoxy. A 1 is preferably Phe, Cyc, Che, Pyr or Dio. The compounds of the formula I preferably contain no more than one of the radicals Bi, Pyd, Pyr, Dio or Dit.

    Bevorzugt sind auch Verbindungen der Formel I sowie aller Teilformeln, in denen A1 ein- oder zweifach durch F oder einfach durch CN substituiertes 1,4-Phenylen bedeutet. Insbesondere sind dies 2-Fluor-1,4-phenylen, 3-Fluor-1,4-phenylen und 2,3-Difluor-1,4-phenylen sowie 2-Cyan-1,4-phenylen und 3-Cyan-1,4-phenylen.Also preferred are compounds of the formula I and all sub-formulas in which A 1 is 1,4-phenylene which is mono- or disubstituted by F or monosubstituted by CN. In particular, these are 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene and 2,3-difluoro-1,4-phenylene as well as 2-cyano-1,4-phenylene and 3-cyano-1 , 4-phenylene.

    Z1 bedeutet bevorzugt eine Einfachbindung, -CO-O-, -O-CO- und -CH2CH2-, in zweiter Linie bevorzugt -CH2O- und -OCH2-. Vorzugsweise ist nur eine der im Molekül vorhandenen Gruppen Z1 von der Einfachbindung verschieden.Z 1 preferably denotes a single bond, -CO-O-, -O-CO- and -CH 2 CH 2 -, in the second place preferably -CH 2 O- and -OCH 2 -. Preferably only one of the Z 1 groups present in the molecule is different from the single bond.

    Falls R einen Alkylrest und/oder einen Alkoxyrest bedeutet, so kann dieser geradkettig oder verzweigt sein. Vorzugsweise ist er geradkettig, hat 2, 3, 4, 5, 6 oder 7 C-Atome und bedeutet demnach bevorzugt Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Ethoxy, Propoxy, Butoxy, Pentoxy, Hexoxy oder Heptoxy, ferner Methyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Methoxy, Octoxy, Nonoxy, Decoxy, Undecoxy, Dodecoxy, Tridecoxy oder Tetradecoxy.If R is an alkyl radical and / or an alkoxy radical, it can be straight or branched. Preferably it is straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly preferably means ethyl, propyl, butyl, pentyl, Hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or Heptoxy, also methyl, octyl, nonyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, Nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

    Oxaalkyl bedeutet vorzugsweise geradkettiges 2-Oxapropyl (= Methoxymethyl), 2- (= Ethoxymethyl) oder 3-Oxabutyl (= 2-Methoxyethyl), 2-, 3- oder 4-Oxapentyl, 2-, 3-, 4- oder 5-Oxahexyl, 2-, 3-, 4-, 5- oder 6-Oxaheptyl, 2-, 3-, 4-, 5-, 6- oder 7-Oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- oder 8-Oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- oder 9-Oxadecyl. Oxaalkyl preferably means straight-chain 2-oxapropyl (= Methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

    Falls R einen Alkylrest bedeutet, in dem eine CH2-Gruppe durch -CH=CH- ersetzt ist, so kann dieser geradkettig oder verzweigt sein. Vorzugsweise ist er geradkettig und hat 2 bis 10 C-Atome. Er bedeutet demnach besonders Vinyl, Prop-1-, oder Prop-2-enyl, But-1-, 2- oder But-3-enyl, Pent-1-, 2-, 3- oder Pent-4-enyl, Hex-1-, 2-, 3-, 4- oder Hex-5-enyl, Hept-1-, 2-, 3-, 4-, 5- oder Hept-6-enyl, Oct-1-, 2-, 3-, 4-, 5-, 6- oder Oct-7-enyl, Non-1-, 2-, 3-, 4-, 5-, 6-, 7- oder Non-8-enyl, Dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- oder Dec-9-enyl.If R is an alkyl radical in which a CH 2 group has been replaced by -CH = CH-, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it means especially vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex -1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, Dec-1 -, 2-, 3-, 4-, 5-, 6-, 7-, 8- or Dec-9-enyl.

    Falls R einen Alkylrest bedeutet, in dem eine CH2-Gruppe durch -O- und eine durch -CO- ersetzt ist, so sind diese bevorzugt benachbart. Somit beeinhalten diese eine Acyloxygruppe -CO-O- oder eine Oxycarbonylgruppe -O-CO-. Vorzugsweise sind diese geradkettig und haben 2 bis 6 C-Atome.If R is an alkyl radical in which one CH 2 group has been replaced by -O- and one has been replaced by -CO-, these are preferably adjacent. Thus, these contain an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. These are preferably straight-chain and have 2 to 6 carbon atoms.

    Sie bedeuten demnach besonders Acetyloxy, Propionyloxy, Butyryloxy, Pentanoyloxy, Hexanoyloxy, Acetyloxymethyl, Propionyloxymethyl, Butyryloxymethyl, Pentanoyloxymethyl, 2-Acetyloxyethyl, 2-Propionyloxyethyl, 2-Butyryloxyethyl, 3-Acetyloxypropyl, 3-Propionyloxypropyl, 4-Acetyloxybutyl, Methoxycarbonyl, Ethoxycarbonyl, Propoxycarbonyl, Butoxycarbonyl, Pentoxycarbonyl, Methoxycarbonylmethyl, Ethoxycarbonylmethyl, Propoxycarbonylmethyl, Butoxycarbonylmethyl, 2-(Methoxycarbonyl)ethyl, 2-(Ethoxycarbonyl)ethyl, 2-(Propoxycarbonyl)ethyl, 3-(Methoxycarbonyl)propyl, 3-(Ethoxycarbonyl)propyl, 4-(Methoxycarbonyl)-butyl. Accordingly, they mean especially acetyloxy, propionyloxy, Butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, Propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, Pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, Propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 4- (methoxycarbonyl) butyl.

    Falls R einen Alkylrest bedeutet, in dem eine CH2-Gruppe durch unsubstituiertes oder substituiertes -CH=CH- und eine benachbarte CH2-Gruppe durch CO oder CO-O oder O-CO-ersetzt ist, so kann dieser geradkettig oder verzweigt sein. Vorzugsweise ist er geradkettig und hat 4 bis 13 C-Atome. Er bedeutet demnach besonders Acryloyloxymethyl, 2-Acryloyloxyethyl, 3-Acryloyloxypropyl, 4-Acryloyloxy butyl, 5-Acryloyloxypentyl, 6-Acryloyloxyhexyl, 7-Acryloyloxyheptyl, 8-Acryloyloxyoctyl, 9-Acryloyloxynonyl, 10-Acryloyloxydecyl, Methacryloyloxymethyl, 2-Methacryloyloxyethyl, 3- Methacryloyloxypropyl, 4-Methacryloyloxybutyl, 5-Methacryloyloxypentyl, 6-Methacryloyloxyhexyl, 7-Methacryloyloxyheptyl, 8-Methacryloyloxyoctyl, 9-Methacryloyloxynonyl.If R is an alkyl radical in which one CH 2 group has been replaced by unsubstituted or substituted -CH = CH- and an adjacent CH 2 group has been replaced by CO or CO-O or O-CO-, this can be straight-chain or branched . It is preferably straight-chain and has 4 to 13 carbon atoms. Accordingly, it means, in particular, acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxy butyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxoyloxoyloxydylmethyl, methacryloyloxoyloxydoxyl, methacryloyloxydoxyl, methacrylate - methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl, 9-methacryloyloxynonyl.

    Verbindungen der Formel I, die über für Polymerisationsreaktionen geeignete Flügelgruppen R verfügen, eignen sich zur Darstellung flüssigkristalliner Polymerer.Compounds of the formula I which are used for polymerization reactions suitable wing groups R are suitable for Representation of liquid crystalline polymers.

    Verbindungen der Formel I mit verzweigten Flügelgruppen R können gelegentlich wegen einer besseren Löslichkeit in den üblichen flüssigkristallinen Basismaterialien von Bedeutung sein, insbesondere aber als chirale Dotierstoffe, wenn sie optisch aktiv sind. Smektische Verbindungen dieser Art eignen sich als Komponenten für ferroelektrische Materialien.Compounds of formula I with branched wing groups R can occasionally due to better solubility in the usual liquid-crystalline base materials of importance be, but especially as chiral dopants if they are optically active. Smectic compounds of this kind are suitable as components for ferroelectric materials.

    Verbindungen der Formel I mit SA-Phasen eignen sich beispielsweise für thermisch adressierte Displays. Compounds of the formula I with S A phases are suitable, for example, for thermally addressed displays.

    Verzweigte Gruppen dieser Art enthalten in der Regel nicht mehr als eine Kettenverzweigung. Bevorzugte verzweigte Reste R sind Isopropyl, 2-Butyl (= 1-Methylpropyl), Isobutyl (= 2-Methylpropyl), 2-Methylbutyl, Isopentyl (= 3-Methylbutyl), 2-Methylpentyl, 3-Methylpentyl, 2-Ethylhexyl, 2-Propylpentyl, Isopropoxy, 2-Methylpropoxy, 2-Methylbutoxy, 3-Methylbutoxy, 2-Methylpentoxy, 3-Methylpentoxy, 2-Ethylhexoxy, 1-Methylhexoxy, 1-Methylheptoxy.Branched groups of this type usually do not contain more than a chain branch. Preferred branched residues R are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, Isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 1-methylheptoxy.

    Falls R einen Alkylrest darstellt, in dem zwei oder mehr CH2-Gruppen durch -O- und/oder -CO-O- ersetzt sind, so kann dieser geradkettig oder verzweigt sein. Vorzugsweise ist er verzweigt und hat 3 bis 12 C-Atome. Er bedeutet demnach besonders Bis-carboxy-methyl, 2,2-Bis-carboxy-ethyl, 3,3-Bis-carboxy-propyl, 4,4-Bis-carboxy-butyl, 5,5-Bis-carboxy-pentyl, 6,6-Bis-carboxy-hexyl, 7,7-Bis-carboxy-heptyl, 8,8-Bis-carboxy-octyl, 9,9-Bis-carboxy-nonyl, 10,10-Bis-carboxy-decyl, Bis-(methoxycarbonyl)-methyl, 2,2-Bis-(methoxycarbonyl)-ethyl, 3,3-Bis-(methoxycarbonyl)-propyl, 4,4-Bis-(methoxycarbonyl)-butyl, 5,5-Bis-(methoxycarbonyl)-pentyl, 6,6-Bis-(methoxycarbonyl)-hexyl, 7,7-Bis-(methoxycarbonyl)-heptyl, 8,8-Bis-(methoxycarbonyl)-octyl, Bis-(ethoxycarbonyl)-methyl, 2,2-Bis-(ethoxycarbonyl)-ethyl, 3,3-Bis-(ethoxycarbonyl)-propyl, 4,4-Bis-(ethoxycarbonyl)-butyl, 5,5-Bis-(ethoxycarbonyl)-hexyl.If R represents an alkyl radical in which two or more CH 2 groups have been replaced by -O- and / or -CO-O-, this can be straight-chain or branched. It is preferably branched and has 3 to 12 carbon atoms. Accordingly, it means especially bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, Bis (methoxycarbonyl) methyl, 2,2-bis (methoxycarbonyl) ethyl, 3,3-bis (methoxycarbonyl) propyl, 4,4-bis (methoxycarbonyl) butyl, 5,5-bis (methoxycarbonyl) pentyl, 6,6-bis (methoxycarbonyl) hexyl, 7,7-bis (methoxycarbonyl) heptyl, 8,8-bis (methoxycarbonyl) octyl, bis (ethoxycarbonyl) methyl, 2,2-bis (ethoxycarbonyl) ethyl, 3,3-bis (ethoxycarbonyl) propyl, 4,4-bis (ethoxycarbonyl) butyl, 5,5-bis (ethoxycarbonyl) hexyl.

    Verbindungen der Formel I, die über für Polykondensationen geeignete Flügelgruppen R verfügen, eignen sich zur Darstellung flüssigkristalliner Polykondensate. Compounds of the formula I which are used for polycondensation suitable wing groups R are suitable for illustration liquid crystalline polycondensates.

    Formel I umfaßt sowohl die Racemate dieser Verbindungen als auch die optischen Antipoden sowie deren Gemische.Formula I includes both the racemates of these compounds also the optical antipodes and their mixtures.

    -(A1-Z1)m- hat vorzugsweise eine der folgenden Bedeutungen:

    Figure 00110001
    - (A 1 -Z 1 ) m - preferably has one of the following meanings:
    Figure 00110001

    Unter diesen Verbindungen der Formel I sowie den Unterformeln sind diejenigen bevorzugt, in denen mindestens einer der darin enthaltenden Reste eine der angegebenen bevorzugten Bedeutungen hat.Among these compounds of formula I and the sub-formulas preferred are those in which at least one of the residues contained therein is one of the preferred Has meanings.

    In den Verbindungen der Formel I sind diejenigen Stereoisomeren bevorzugt, in denen die Ringe Cyc und Piperidin trans-1,4-disubstituiert sind. Diejenigen der vorstehend genannten Formeln, die eine oder mehrere Gruppen Pyd, Pyr und/oder Dio enthalten, umschließen jeweils die beiden 2,5-Stellungsisomeren. In the compounds of formula I are those stereoisomers preferred, in which the rings Cyc and piperidine are trans-1,4-disubstituted. Those of the above mentioned formulas, the one or more groups Pyd, Pyr and / or Dio included, each enclose the two 2,5-position isomers.

    Die 1,4-Cyclohexenylen-Gruppe hat vorzugsweise folgende Strukturen:

    Figure 00120001
    The 1,4-cyclohexenylene group preferably has the following structures:
    Figure 00120001

    Die Verbindungen der Formel I werden nach an sich bekannten Methoden dargestellt, wie sie in der Literatur (z.B. in den Standardwerken wie Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart Bd IX, S. 867 ff.) beschrieben sind, und zwar unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann man auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen.The compounds of formula I are known per se Methods presented as they are in the literature (e.g. in the Standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart Vol IX, pp. 867 ff.) are described, under reaction conditions that are known and suitable for the implementations mentioned. It is also possible to do so from those known per se, but not here make use of the variants mentioned.

    Die Verbindungen der Formel I können z.B. hergestellt werden, indem man entsprechende Aldehyde (die ihrerseits aus entsprechenden, bekannten Nitrilen nach Routinemethoden zugänglich sind) mit SF4 umsetzt.The compounds of the formula I can be prepared, for example, by reacting corresponding aldehydes (which in turn can be obtained from corresponding, known nitriles by routine methods) with SF 4 .

    Ausgangsstoffe können gewünschtenfalls auch in situ gebildet werden, derart, daß man sie aus dem Reaktionsgemisch nicht isoliert, sondern sofort weiter zu den Verbindungen der Formel I umsetzt.If desired, starting materials can also be formed in situ be such that you can not from the reaction mixture isolated, but immediately continue to the connections of the Formula I implements.

    Verbindungen der Formel I, die ansonsten der Formel I entsprechen, aber an Stelle von 1,4-Phenylenresten 1,4-Cyclo-hexenylenreste besitzen, können zum Beispiel mit DDQ (Dichlordicyanobenzochinon) in einem geeigneten Lösungsmittel oxidiert werden. Compounds of the formula I which otherwise correspond to the formula I but instead of 1,4-phenylene residues 1,4-cyclo-hexenylene residues with DDQ (dichlorodicyanobenzoquinone) in a suitable solvent be oxidized.

    Ester der Formel I können auch durch Veresterung entsprechender Carbonsäuren (oder ihren reaktionsfähigen Derivate) mit Alkoholen bzw. Phenolen (oder ihren reaktionsfähigen Derivaten) oder nach der DCC-Methode (DCC = Dicyclohexylcarbodiimid) erhalten werden.Esters of the formula I can also be correspondingly esterified Carboxylic acids (or their reactive derivatives) with alcohols or phenols (or their reactive Derivatives) or by the DCC method (DCC = dicyclohexylcarbodiimide) be preserved.

    Die entsprechenden Carbonsäuren und Alkohole bzw. Phenole sind bekannt oder können in Analogie zu bekannten Verfahren hergestellt werden.The corresponding carboxylic acids and alcohols or phenols are known or can be used in analogy to known methods getting produced.

    Als reaktionsfähige Derivate der genannten Carbonsäuren eignen sich insbesondere die Säurehalogenide, vor allem die Chloride und Bromide, ferner die Anhydride, z.B. auch gemischte Anhydride, Azide oder Ester, insbesondere Alkylester mit 1-4 C-Atomen in der Alkylgruppe.As reactive derivatives of the carboxylic acids mentioned acid halides are particularly suitable, especially those Chlorides and bromides, furthermore the anhydrides, e.g. also mixed anhydrides, azides or esters, especially alkyl esters with 1-4 C atoms in the alkyl group.

    Als reaktionsfähige Derivate der genannten Alkohole bzw. Phenole kommen insbesondere die entsprechenden Metallalkoholate bzw. Phenolate, vorzugsweise eines Alkalimetalls wie Natrium oder Kalium, in Betracht.As reactive derivatives of the alcohols mentioned or Phenols come in particular the corresponding metal alcoholates or phenolates, preferably an alkali metal such as Sodium or potassium.

    Die Veresterung wird vorteilhaft in Gegenwart eines inerten Lösungsmittels durchgeführt. Gut geeignet sind insbesondere Ether wie z.B. Diethylether, Di-n-butylether, THF, Dioxan oder Anisol, Ketone wie z.B. Aceton, Butanon oder Cyclohexanon, Amide wie z.B. DMF oder Phosphorsäurehexamethyltriamid, Kohlenwasserstoffe wie z.B. Benzol, Toluol oder Xylol, Halogenkohlenwasserstoffe wie z.B. Tetrachlorkohlenstoff, Dichlormethan oder Tetrachlorethylen und Sulfoxide wie z.B. Dimethylsulfoxid oder Sulfolan.The esterification is advantageous in the presence of an inert Solvent carried out. Are particularly suitable Ethers such as Diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as Acetone, butanone or cyclohexanone, Amides such as DMF or phosphoric acid hexamethyl triamide, Hydrocarbons such as Benzene, toluene or xylene, Halogenated hydrocarbons such as Carbon tetrachloride, Dichloromethane or tetrachlorethylene and sulfoxides such as e.g. Dimethyl sulfoxide or sulfolane.

    Ether der Formel I sind durch Veretherung entsprechender Hydroxyverbindungen, vorzugsweise entsprechender Phenole, erhältlich, wobei die Hydroxyverbindung zweckmäßig zunächst in ein entsprechendes Metallderivat, z.B. durch Behandeln mit NaH, NaNH2, NaOH, KOH, Na2CO3 oder K2CO3 in das entsprechende Alkalimetallalkoholat oder Alkalimetallphenolat übergeführt wird. Dieses kann dann mit dem entsprechenden Alkylhalogenid, -sulfonat oder Dialkylsulfat umgesetzt werden, zweckmäßig in einem inerten Lösungsmittel wie z.B. Aceton, 1,2-Dimethoxyethan, DMF oder Dimethylsulfoxid oder auch mit einem Überschuß an wäßriger oder wäßrig-alkoholischer NaOH oder KOH bei Temperaturen zwischen etwa 20° und 100°.Ethers of the formula I can be obtained by etherification of corresponding hydroxy compounds, preferably corresponding phenols, the hydroxy compound expediently first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 corresponding alkali metal alcoholate or alkali metal phenolate is converted. This can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 °.

    Dioxanderivate bzw. Dithianderivate der Formel I werden zweckmäßig durch Reaktion eines entsprechenden Aldehyds (oder eines seiner reaktionsfähigen Derivate) mit einem entsprechenden 1,3-Diol (oder einem seiner reaktionsfähigen Derivate) bzw. einem entsprechenden 1,3-Dithiol hergestellt, vorzugsweise in Gegenwart eines inerten Lösungsmittels wie z.B. Benzol oder Toluol und/oder eines Katalysators, z.B. einer starken Säure wie Schwefelsäure, Benzol- oder p-Toluolsulfonsäure, bei Temperaturen zwischen etwa 20° und etwa 150°, vorzugsweise zwischen 80° und 120°. Als reaktionsfähige Derivate der Ausgangsstoffe eignen sich in erster Linie Acetale.Dioxane derivatives or dithiane derivatives of the formula I are expediently by reaction of an appropriate aldehyde (or one of its reactive derivatives) with one corresponding 1,3-diol (or one of its reactive Derivatives) or a corresponding 1,3-dithiol, preferably in the presence of an inert solvent such as e.g. Benzene or toluene and / or a catalyst e.g. a strong acid such as sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between about 20 ° and about 150 °, preferably between 80 ° and 120 °. As responsive Derivatives of the starting materials are primarily suitable Acetals.

    Die genannten Aldehyde und 1,3-Diole bzw. 1,3-Dithiole sowie ihre reaktionsfähigen Derivate sindzum Teil bekannt, zum Teil können sie ohne Schwierigkeiten nach Standardverfahren der Organischen Chemie aus literaturbekannten Verbindungen hergestellt werden. Beispielsweise sind die Aldehyde durch Oxydation entsprechender Alkohole oder durch Reduktion von Nitrilen oder entsprechenden Carbonsäuren oder ihrer Derivate, die Diole durch Reduktion entsprechender Diester und die Dithiole durch Umsetzung entsprechender Dihalogenide mit NaSH erhältlich.The aldehydes and 1,3-diols or 1,3-dithiols mentioned and some of their reactive derivatives are known to: Part of it can be done without difficulty using standard procedures of organic chemistry from compounds known from the literature getting produced. For example, the aldehydes are through Oxidation of appropriate alcohols or by reduction of Nitriles or corresponding carboxylic acids or their derivatives, the diols by reducing the corresponding diesters and the dithiols by reacting appropriate dihalides with NaSH available.

    Die erfindungsgemäßen Verbindungen mit L1 = F können z.B. hergestellt werden, indem man eine Verbindung der Formel II,

    Figure 00150001
    worin R, A1, Z1, L2 und m die angegebene Bedeutung haben, gemäß folgenden Reaktionsschemata umsetzt:
    Figure 00150002
    Figure 00160001
    The compounds according to the invention with L 1 = F can be prepared, for example, by using a compound of the formula II
    Figure 00150001
    where R, A 1 , Z 1 , L 2 and m have the meaning given, according to the following reaction schemes:
    Figure 00150002
    Figure 00160001

    Weitere Synthesemethoden sind für den Fachmann augenscheinlich. Beispielsweise können in 5-Position entsprechend substituierte 1,3-Difluorbenzol-Verbindungen oder monofluorierte Analoga (L2 = H) gemäß obigem Schema in die 2-substituierten 1,3-Difluorverbindungen oder monofluorierte Analoga (L2 = H) überführt werden und der Rest R-(A1-Z1)m-anschließend durch in der Flüssigkristallchemie gebräuchliche Reaktionen (z.B. Veresterung, Veretherung oder Kopplungen z.B. gemäß der Artikel E. Poetsch, Kontakte (Darmstadt) 1988 (2), S. 15) eingeführt werden oder umgekehrt.Other synthetic methods are obvious to the person skilled in the art. For example (2 L = H) according to the above scheme in the can 2-substituted in 5-position appropriately substituted 1,3-difluorobenzene compounds or mono-fluorinated analogues 1,3-difluoro compounds or mono-fluorinated analogues (L 2 = H) are transferred and The rest R- (A 1 -Z 1 ) m - are subsequently introduced or by reactions customary in liquid crystal chemistry (for example esterification, etherification or coupling, for example according to the article E. Poetsch, contacts (Darmstadt) 1988 (2), p. 15) vice versa.

    Die Verbindungen der Formel II können beispielsweise nach folgenden Syntheseschemata hergestellt werden:

    Figure 00170001
    Figure 00180001
    Figure 00190001
    The compounds of the formula II can be prepared, for example, according to the following synthesis schemes:
    Figure 00170001
    Figure 00180001
    Figure 00190001

    Die Ausgangsmaterialien sind entweder bekannt oder können in Analogie zu bekannten Verbindungen hergestellt werden.The starting materials are either known or can be found in Analogy to known compounds.

    Ester der Formel I können auch durch Veresterung entsprechender Carbonsäuren (oder ihrer reaktionsfähigen Derivate) mit Alkoholen bzw. Phenolen (oder ihren reaktionsfähigen Derivaten) oder nach der DCC-Methode (DCC = Dicyclohexylcarbodiimid) erhalten werden.Esters of the formula I can also be correspondingly esterified Carboxylic acids (or their reactive derivatives) with alcohols or phenols (or their reactive Derivatives) or by the DCC method (DCC = dicyclohexylcarbodiimide) be preserved.

    Die entsprechenden Carbonsäuren und Alkohole bzw. Phenole sind bekannt oder können in Analogie zu bekannten Verfahren oder auch durch Umsetzung von metalliertem II mit geeigneten Elektrophilen (B(OH)3/H2O2 bzw. CO2) hergestellt werden.The corresponding carboxylic acids and alcohols or phenols are known or can be prepared analogously to known processes or also by reacting metalated II with suitable electrophiles (B (OH) 3 / H 2 O 2 or CO 2 ).

    Die Synthese einiger besonders bevorzugter Verbindungen ist im folgenden näher angegeben (Y = H oder F):

    Figure 00200001
    The synthesis of some particularly preferred compounds is specified in more detail below (Y = H or F):
    Figure 00200001

    In einem weiteren Verfahren zur Herstellung der Verbindungen der Formel I setzt man ein Arylhalogenid mit einem Olefin um in Gegenwart eines tertiären Amins und eines Palladiumkatalysators (vgl. R.F. Heck, Acc. Chem. Res. 12 (1979) 146). Geeignete Arylhalogenide sind beispielsweise Chloride, Bromide und Iodide, insbesondere Bromide und Iodide. Die für das Gelingen der Kupplungsreaktion erforderlichen tertiären Amine, wie z.B. Triethylamin, eignen sich auch als Lösungsmittel. Als Palladiumkatalysatoren sind beispielsweise dessen Salze, insbesondere Pd(II)-acetat, mit organischen Phosphor(III)-Verbindungen wie z.B. Triarylphosphanen geeignet. Man kann dabei in Gegenwart oder Abwesenheit eines inerten Lösungsmittels bei Temperaturen zwischen etwa 0° und 150°, vorzugsweise zwischen 20° und 100°, arbeiten; als Lösungsmittel kommen z.B. Nitrile wie Acetonitril oder Kohlenwasserstoffe wie Benzol oder Toluol in Betracht. Die als Ausgangsstoffe eingesetzten Arylhalogenide und Olefine sind vielfach im Handel erhältlich oder können nach literaturbekannten Verfahren hergestellt werden, beispielsweise durch Halogenierung entsprechender Stammverbindungen bzw. durch Eliminierungsreaktionen an entsprechenden Alkoholen oder Halogeniden.In a further process for the preparation of the compounds of the formula I, an aryl halide is reacted with an olefin in the presence of a tertiary amine and a palladium catalyst (cf. RF Heck, Acc. Chem. Res. 12 (1979) 146). Suitable aryl halides are, for example, chlorides, bromides and iodides, in particular bromides and iodides. The tertiary amines required for the coupling reaction to succeed, such as triethylamine, are also suitable as solvents. Suitable palladium catalysts are, for example, its salts, in particular Pd (II) acetate, with organic phosphorus (III) compounds such as, for example, triarylphosphines. You can work in the presence or absence of an inert solvent at temperatures between about 0 ° and 150 °, preferably between 20 ° and 100 °; Examples of suitable solvents are nitriles such as acetonitrile or hydrocarbons such as benzene or toluene. The aryl halides and olefins used as starting materials are commercially available in many cases or can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.

    Auf diese Weise sind beispielsweise Stilbenderivate herstellbar. Die Stilbene können weiterhin hergestellt werden durch Umsetzung eines 4-substituierten Benzaldehyds mit einem entsprechenden Phosphorylid nach Wittig. Man kann aber auch Tolane der Formel I herstellen, indem man anstelle des Olefins monosubstituiertes Acetylen einsetzt (Synthesis 627 (1980) oder Tetrahedron Lett. 27, 1171 (1986)).In this way, stilbene derivatives can be produced, for example. The stilbenes can also be produced by reacting a 4-substituted benzaldehyde with a corresponding phosphorylide according to Wittig. However, tolanes of the formula I can also be prepared by using monosubstituted acetylene instead of the olefin (Synthesis 627 (1980) or Tetrahedron Lett. 27 , 1171 (1986)).

    Weiterhin können zur Kopplung von Aromaten Arylhalogenide mit Arylzinkverbindungen umgesetzt werden. Bevorzugt werden diese Reaktionen unter Zusatz eines Katalysators wie z.B. eines Palladium(O)komplexes in inerten Lösungsmitteln wie Kohlenwasserstoffen bei hohen Temperaturen, z.B. in siedendem Xylol, unter Schutzgas durchgeführt.Aryl halides can also be used to couple aromatics be implemented with aryl zinc compounds. To be favoured these reactions with the addition of a catalyst such as e.g. of a palladium (O) complex in inert solvents such as Hydrocarbons at high temperatures, e.g. in boiling Xylene, carried out under protective gas.

    Kopplungen von Alkinyl-Verbindungen mit Arylhalogeniden können analog dem von A.O. King, E. Negishi, F.J. Villani und A. Silveira in J.Org.Chem. 43, 358 (1978) beschriebenen Verfahren durchgeführt werden.Couplings of alkynyl compounds with aryl halides can be analogous to that of AO King, E. Negishi, FJ Villani and A. Silveira in J.Org.Chem. 43 , 358 (1978).

    Tolane der Formel I können auch über die Fritsch-Buttenberg-Wiechell-Umlagerung (Ann. 279, 319, 332, 1984) hergestellt werden, bei der 1,1-Diaryl-2-halogenethylene umgelagert werden zu Diarylacetylenen in Gegenwart starker Basen.Tolanes of the formula I can also be prepared via the Fritsch-Buttenberg-Wiechell rearrangement (Ann. 279 , 319, 332, 1984), in which 1,1-diaryl-2-halogenethylenes are rearranged to diarylacetylenes in the presence of strong bases.

    Tolane der Formel I können auch hergestellt werden, indem man die entsprechenden Stilbene bromiert und anschließend einer Dehydrohalogenierung unterwirft. Dabei kann man an sich bekannte, hier nicht näher erwähnte Varianten dieser Umsetzung anwenden.Tolanes of formula I can also be prepared by the corresponding style level is brominated and then subject to dehydrohalogenation. You can do that well-known, not mentioned variants of this Apply implementation.

    Ether der Formel I sind durch Veretherung entsprechender Hydroxyverbindungen, vorzugsweise entsprechender Phenole, erhältlich, wobei die Hydroxyverbindung zweckmäßig zunächst in ein entsprechendes Metallderivat, z.B. durch Behandeln mit NaH, NaNH2, NaOH, KOH, Na2CO3 oder K2CO3 in das entsprechende Alkalimetallalkoholat oder Alkalimetallphenolat übergeführt wird. Dieses kann dann mit dem entsprechenden Alkylhalogenid, -sulfonat oder Dialkylsulfat umgesetzt werden, zweckmäßig in einem inerten Lösungsmittel, wie z.B. Aceton, 1,2-Dimethoxyethan, DMF oder Dimethylsulfoxid oder auch mit einem Überschuß an wäßriger oder wäßrig-alkoholischer NaOH oder KOH bei Temperaturen zwischen etwa 20° und 100°.Ethers of the formula I can be obtained by etherification of corresponding hydroxy compounds, preferably corresponding phenols, the hydroxy compound expediently first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 corresponding alkali metal alcoholate or alkali metal phenolate is converted. This can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 °.

    Ausgehend von dem käuflichen

    Figure 00230001
    lassen sich die Verbindungen nach an und für sich bekannten Methoden darstellen. Außer den im nachstehenden Schema aufgeführten Verknüpfungsmöglichkeiten ergeben sich auch analoge Syntheseverfahren über Friedel-Crafts-Acylierung oder Wittig-Reaktion mit nachfolgender Reduktion bzw. Hydrierung für den Aufbau der CH2-CH2 verknüpften Substanzen.Based on the commercial
    Figure 00230001
    the compounds can be prepared according to methods known per se. In addition to the linkage options listed in the diagram below, there are also analogous synthetic processes via Friedel-Crafts acylation or Wittig reaction with subsequent reduction or hydrogenation for the synthesis of the CH 2 -CH 2 linked substances.

    Die

    Figure 00240001
    enthaltenden Verbindungen lassen sich über eine Chlorierung mittels PCl5 zu
    Figure 00240002
    und nachfolgende HCl-Eliminierung mittels Base in die Acetylene umwandeln. Die Transformation der -CH=CH- verbrückten Substanzen, die über Heck-Kopplung oder Wittig-Reaktion herstellbar sind, gelingt nach herkömmlicher Weise z.B. mittels Bromierung und doppelter HBr-Abspaltung.The
    Figure 00240001
    containing compounds can be chlorinated using PCl 5
    Figure 00240002
    and convert the subsequent HCl elimination into the acetylene using a base. The transformation of the -CH = CH- bridged substances, which can be produced via Heck coupling or Wittig reaction, is accomplished in a conventional manner, for example by means of bromination and double HBr elimination.

    Die Einführung der Carboxylat-Gruppe gelingt in Analogie zur Einführung der CH2CH2-Gruppe (vergl. Verbindung 7, nachstehendes Formelschema) mittels CO2. Die intermediär gebildeten Säuren lassen sich mit den entsprechenden Phenolen verestern, die aus 1 gemäß Syntheseschritt ba darstellbar sind.

    Figure 00250001
    Figure 00260001
    The carboxylate group is introduced in analogy to the introduction of the CH 2 CH 2 group (cf. compound 7, formula scheme below) using CO 2 . The intermediately formed acids can be esterified with the corresponding phenols, which can be prepared from 1 according to synthesis step ba.
    Figure 00250001
    Figure 00260001

    Die Verbindungen der Formel I, worin L1 und L2 F bedeuten und der mit

    Figure 00270001
    verknüpfte Rest A1 1,4-Cyclohexylen bedeutet, können nach folgendem Schema hergestellt werden:
    Figure 00270002
    The compounds of formula I, wherein L 1 and L 2 are F and with
    Figure 00270001
    linked radical A 1 means 1,4-cyclohexylene, can be prepared according to the following scheme:
    Figure 00270002

    Die Verbindung 8 läßt sich gemäß d) zu 12 und analog e) zu 13 umsetzen. 12 wird mittels Vinylbromid gemäß bc) und 13 mittels Divinylzink gemäß c) zu 14 umgesetzt. 15 läßt sich aus 12 und 1 mittels Kreuzkopplung gemäß h) erhalten oder aus 13 und 3 durch Kreuzkopplung.The compound 8 can be according to d) to 12 and analogous to e) 13 implement. 12 is by means of vinyl bromide according to bc) and 13 converted to 14 using divinyl zinc according to c). 15 can obtained from 12 and 1 by means of cross coupling according to h) or from 13 and 3 by cross coupling.

    Die CH=CH-Gruppierung ist in die CH2-CH2 oder -C≡C-Gruppierung überführbar.The CH = CH grouping can be converted into the CH 2 -CH 2 or -C≡C grouping.

    Die Einführung der Endgruppierung

    Figure 00280001
    gelingt entweder durch Verwendung eines Kopplungsschrittes mit
    Figure 00280003
    (D = Hal, m,
    Figure 00280002
    oder durch Einführung von CHF2 in Verbindungen mit der Endgruppierung
    Figure 00280004
    The introduction of the final grouping
    Figure 00280001
    succeeds either by using a coupling step
    Figure 00280003
    (D = Hal, m,
    Figure 00280002
    or by introducing CHF 2 in connection with the final grouping
    Figure 00280004

    Die Herstellung von ebenfalls die CO2 und/oder C≡C Zwischenglieder enthaltenden Verbindungen läßt sich sinngemäß nach analogen Formelschemata durchführen. The preparation of compounds also containing the CO 2 and / or C≡C intermediate members can be carried out analogously according to analogous formula schemes.

    Einige besonders bevorzugt, kleinere Gruppen von Verbindungen der Formel I sind im folgenden angegeben:

    Figure 00290001
    Figure 00300001
    Figure 00310001
    Some particularly preferred, smaller groups of compounds of formula I are given below:
    Figure 00290001
    Figure 00300001
    Figure 00310001

    Die erfindungsgemäßen flüssigkristallinen Medien enthalten vorzugsweise neben einer oder mehreren erfindungsgemäßen Verbindungen als weitere Bestandteile 2 bis 40, insbesondere 4 bis 30 Komponenten. Ganz besonders bevorzugt enthalten diese Medien neben einer oder mehreren erfindungsgemäßen Verbindungen 7 bis 25 Komponenten. Diese weiteren Bestandteile werden vorzugsweise ausgewählt aus nematischen oder nematogenen (monotropen oder isotropen) Substanzen, insbesondere Substanzen aus den Klassen der Azoxybenzole, Benzylidenaniline, Biphenyle, Terphenyle, Phenyl- oder Cyclohexylbenzoate, Cyclohexan-carbonsäurephenyl- oder cyclohexyl-ester, Phenyl- oder Cyclohexylester der Cyclohexylbenzoesäure, Phenyl- oder Cyclohexylester der Cyclohexylcyclohexancarbonsäure, Cyclohexylphenylester der Benzoesäure, der Cyclohexancarbonsäure, bzw. der Cyclohexylcyclohexancarbonsäure, Phenylcyclohexane, Cyclohexylbiphenyle, Phenylcyclohexylcyclohexane, Cyclohexylcyclohexane Cyclohexylcyclohexene, Cyclohexylcyclohexylcyclohexene, 1,4-Bis-cyclohexylbenzole, 4,4'-Bis-cyclohexylbiphenyle, Phenyl- oder Cyclohexylpyrimidine, Phenyl- oder Cyclohexylpyridine, Phenyl- oder Cyclohexyldioxane, Phenyl- oder Cyclohexyl-1,3-dithiane, 1,2-Diphenylethane, 1,2-Dicyclohexylethane, 1-Phenyl-2-cyclohexylethane, 1-Cyclohexyl-2-(4-phenyl-cyclohexyl)-ethane, 1-Cyclohexyl-2-biphenylylethane, 1-Phenyl-2-cyclohexylphenylethane, gegebenenfalls halogenierten Stilbene, Benzylphenylether, Tolane und substituierten Zimtsäuren. Die 1,4-Phenylengruppen in diesen Verbindungen können auch fluoriert sein.The liquid-crystalline media according to the invention contain preferably in addition to one or more of the invention Compounds as further components 2 to 40, in particular 4 to 30 components. Very particularly preferably included these media in addition to one or more of the invention Connections 7 to 25 components. These other ingredients are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular Substances from the classes of azoxybenzenes, Benzylidenanilines, biphenyls, terphenyls, phenyl or Cyclohexylbenzoate, cyclohexane-carboxylic acid phenyl or cyclohexyl ester, phenyl or cyclohexyl ester of cyclohexylbenzoic acid, Phenyl or cyclohexyl ester of cyclohexylcyclohexane carboxylic acid, Cyclohexylphenyl ester of Benzoic acid, cyclohexane carboxylic acid or cyclohexylcyclohexane carboxylic acid, Phenylcyclohexanes, cyclohexylbiphenyls, Phenylcyclohexylcyclohexane, cyclohexylcyclohexane Cyclohexylcyclohexenes, cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, Phenyl or cyclohexyl pyrimidines, phenyl or Cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or Cyclohexyl-1,3-dithiane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenyl-cyclohexyl) ethane, 1-cyclohexyl-2-biphenylylethane, 1-phenyl-2-cyclohexylphenylethane, optionally halogenated stilbenes, benzylphenyl ether, tolanes and substituted cinnamic acids. The 1,4-phenylene groups in these compounds can also be fluorinated.

    Die wichtigsten als weitere Bestandteile erfindungsgemäßer Medien in Frage kommenden Verbindungen lassen sich durch die Formeln 1, 2, 3, 4, und 5 charakterisieren: R'-L-E-R'' R'-L-COO-E-R'' R'-L-OOC-E-R'' R'-L-CH2CH2-E-R'' R'-L-C≡C-E-R'' The most important compounds which are possible as further constituents of media according to the invention can be characterized by the formulas 1, 2, 3, 4 and 5: R'-LE-R '' R'-L-COO-E-R '' R'-L-OOC-E-R '' R'-L-CH 2 CH 2 -E-R '' R'-LC≡CE-R ''

    In den Formeln 1, 2, 3, 4 und 5 bedeuten L und E, die gleich oder verschieden sein können, jeweils unabhängig voneinander einen bivalenten Rest aus der aus -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- und -G-Cyc- sowie deren Spiegelbilder gebildeten Gruppe, wobei Phe unsubstituiertes oder durch Fluor substituiertes 1,4-Phenylen, Cyc trans-1,4-Cyclohexylen oder 1,4-Cyclohexenylen, Pyr Pyrimidin-2,5-diyl oder Pyridin-2,5-diyl, Dio 1,3-Dioxan-2,5-diyl und G 2-(trans-1,4-Cyclohexyl)-ethyl, Pyrimidin-2,5-diyl, Pyridin-2,5-diyl oder 1,3-Dioxan-2,5-diyl bedeuten.In formulas 1, 2, 3, 4 and 5, L and E mean the same or can be different, each independently a bivalent residue from the from -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well whose mirror images formed group, whereby Phe unsubstituted or fluorine-substituted 1,4-phenylene, Cyc trans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr Pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio 1,3-dioxane-2,5-diyl and G 2- (trans-1,4-cyclohexyl) ethyl, pyrimidine-2,5-diyl, Pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl mean.

    Vorzugsweise ist einer der Reste L und E Cyc, Phe oder Pyr. E ist vorzugsweise Cyc, Phe oder Phe-Cyc. Vorzugsweise enthalten die erfindungsgemäßen Medien eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin L und E ausgewählt sind aus der Gruppe Cyc, Phe und Pyr und gleichzeitig eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin einer der Reste L und E ausgewählt ist aus der Gruppe Cyc, Phe und Pyr und der andere Rest ausgewählt ist aus der Gruppe -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- und -G-Cyc-, und gegebenenfalls eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin die Reste L und E ausgewählt sind aus der Gruppe -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- und -G-Cyc-.One of the radicals L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. Preferably the media according to the invention contain one or more Components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein L and E are selected from the group Cyc, Phe and Pyr and simultaneously one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein one of the radicals L and E is selected from selected from the group Cyc, Phe and Pyr and the other residue is from the group -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein the residues L and E are selected from the Group -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-.

    R' und R'' bedeuten in den Verbindungen der Teilformeln 1a, 2a, 3a, 4a und 5a jeweils unabhängig voneinander Alkyl, Alkenyl, Alkoxy, Alkenyloxy oder Alkanoyloxy mit bis zu 8 Kohlenstoffatomen. Bei den meisten dieser Verbindungen sind R' und R'' voneinander verschieden, wobei einer dieser Reste meist Alkyl oder Alkenyl ist. In den Verbindungen der Teilformeln 1b, 2b, 3b, 4b und 5b bedeutet R'' -CN, -CF3, F, Cl oder -NCS; R hat dabei die bei den Verbindungen der Teilformeln 1a bis 5a angegebene Bedeutung und ist vorzugsweise Alkyl oder Alkenyl. Aber auch andere Varianten der vorgesehenen Substituenten in den Verbindungen der Formeln 1, 2, 3, 4 und 5 sind gebräuchlich. Viele solcher Substanzen oder auch Gemische davon sind im Handel erhältlich. Alle diese Substanzen sind nach literaturbekannten Methoden oder in Analogie dazu erhältlich.In the compounds of the sub-formulas 1a, 2a, 3a, 4a and 5a, R 'and R''each independently represent alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. In most of these compounds, R 'and R''are different from one another, one of these radicals usually being alkyl or alkenyl. In the compounds of the sub-formulas 1b, 2b, 3b, 4b and 5b, R ″ is -CN, -CF 3 , F, Cl or -NCS; R has the meaning given for the compounds of the partial formulas 1a to 5a and is preferably alkyl or alkenyl. However, other variants of the proposed substituents in the compounds of the formulas 1, 2, 3, 4 and 5 are also common. Many such substances or mixtures thereof are commercially available. All of these substances can be obtained by methods known from the literature or by analogy.

    Die erfindungsgemäßen Medien enthalten vorzugsweise neben Komponenten aus der Gruppe der Verbindungen 1a, 2a, 3a, 4a und 5a (Gruppe 1) auch Komponenten aus der Gruppe der Verbindungen 1b, 2b, 3b, 4b und 5b (Gruppe 2), deren Anteile vorzugsweise wie folgt sind:

  • Gruppe 1: 20 bis 90 %, insbesondere 30 bis 90%,
  • Gruppe 2: 10 bis 80 %, insbesondere 10 bis 50 %,
    wobei die Summe der Anteile der erfindungsgemäßen Verbindungen und der Verbindungen aus den Gruppen 1 und 2 bis zu 100 % ergeben.
    • In addition to components from the group of compounds 1a, 2a, 3a, 4a and 5a (group 1), the media according to the invention preferably also contain components from the group of compounds 1b, 2b, 3b, 4b and 5b (group 2), the proportions of which are preferably as follows are:
  • Group 1: 20 to 90%, in particular 30 to 90%,
  • Group 2: 10 to 80%, in particular 10 to 50%,
    the sum of the proportions of the compounds according to the invention and of the compounds from groups 1 and 2 giving up to 100%.

    • Die erfindungsgemäßen Medien enthalten vorzugsweise 1 bis 40 %, insbesondere vorzugsweise 5 bis 30 % an erfindungsgemäßen Verbindungen. Weiterhin bevorzugt sind Medien, enthaltend mehr als 40 %, insbesondere 45 bis 90 % an erfindungsgemäßen Verbindungen. Die Medien enthalten vorzugsweise drei, vier oder fünf erfindungsgemäße Verbindungen. The media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of the invention Links. Media containing are also preferred more than 40%, in particular 45 to 90%, of the invention Links. The media preferably contain three, four or five compounds according to the invention.

    Die Herstellung der erfindungsgemäßen Medien erfolgt in an sich üblicher Weise. In der Regel werden die Komponenten ineinander gelöst, zweckmäßig bei erhöhter Temperatur. Durch geeignete Zusätze können die flüssigkristallinen Phasen nach der Erfindung so modifiziert werden, daß sie in allen bisher bekannt gewordenen Arten von Flüssigkristallanzeigeelementen verwendet werden können. Derartige Zusätze sind dem Fachmann bekannt und in der Literatur ausführlich beschrieben (H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). Beispielsweise können pleochroitische Farbstoffe zur Herstellung farbiger Guest-Host-Systeme oder Substanzen zur Veränderung der dielektrischen Anisotropie, der Viskosität und/oder der Orientierung der nematischen Phasen zugesetzt werden.The media according to the invention are produced in yourself in the usual way. Usually the components dissolved in one another, expediently at elevated temperature. By The liquid-crystalline phases can be followed by suitable additives the invention can be modified so that it has been used in all known types of liquid crystal display elements can be used. Such additives are known to the person skilled in the art known and described in detail in the literature (H. Kelker / R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic Dyes for the production of colored guest-host systems or Substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic Phases are added.

    Die folgenden Beispiele sollen die Erfindung erläutern, ohne sie zu begrenzen. Vor- und nachstehend bedeuten Potenzangaben Gewichtsprozent. Alle Temperaturen sind in Grad Celsius angegeben. Fp. bedeutet Schmelzpunkt Kp = Klärpunkt. Ferner bedeuten K = kristalliner Zustand, N = nematische Phase, S = smektische Phase und I = isotrope Phase. Die Angaben zwischen diesen Symbolen stellen die Übergangstemperaturen dar. n bedeutet optische Anisotropie (589 nm, 20 °C) und die Viskosität (mm2/sec) wurde bei 20 °C bestimmt.The following examples are intended to illustrate the invention without limiting it. Above and below, potency data mean percent by weight. All temperatures are given in degrees Celsius. Mp. Means melting point Kp = clearing point. Furthermore, K = crystalline state, N = nematic phase, S = smectic phase and I = isotropic phase. The data between these symbols represent the transition temperatures. N means optical anisotropy (589 nm, 20 ° C.) and the viscosity (mm 2 / sec) was determined at 20 ° C.

    "Übliche Aufarbeitung" bedeutet: man gibt gegebenenfalls Wasser hinzu, extrahiert mit Methylenchlorid, Diethylether oder Toluol, trennt ab, trocknet die organische Phase, dampft ein und reinigt dar Produkt durch Destillation unter reduziertem Druck oder Kristallisation und/oder Chromatographie. Folgende Abkürzungen werden verwendet:

    DAST
    Diethylaminoschwefeltrifluorid
    DCC
    Dicyclohexylcarbodiimid
    DDQ
    Dichlordicyanobenzochinon
    DIBALH
    Diisobutylaluminiumhydrid
    KOT
    Kalium-tertiär-butanolat
    THF
    Tetrahydrofuran
    pTSOH
    p-Toluolsulfonsäure
    TMEDA
    Tetramethylethylendiamin
    "Customary work-up" means: water is optionally added, extracted with methylene chloride, diethyl ether or toluene, separated, the organic phase is dried, evaporated and the product is purified by distillation under reduced pressure or crystallization and / or chromatography. The following abbreviations are used:
    DAST
    Diethylamino sulfur trifluoride
    DCC
    Dicyclohexylcarbodiimide
    DDQ
    Dichlorodicyanobenzoquinone
    DIBALH
    Diisobutyl aluminum hydride
    Droppings
    Potassium tertiary butoxide
    THF
    Tetrahydrofuran
    pTSOH
    p-toluenesulfonic acid
    TMEDA
    Tetramethylethylenediamine

    Beispiel 1example 1

    Ein Gemisch von 9,2 g 2,6-Difluor-4-2-(p-ethoxyphenyl)-ethyl-phenylboronsäure (hergestellt durch Umsetzung von 3,5-Difluorbenzaldehyd mit p-Ethoxybenzyltriphenylphosphoniumjodid nach Wittig und nachfolgender Hydrierung des erhaltenen Styrolderivates an Pd/C), 6,5 g 1-Brom-4-difluormethylbenzol, 38 ml 2 M wässeriger Na2CO3-Lsg., 0,6 g Tetrakis(triphenylphosphin)palladium-(0) und 75 ml Toluol wird zwei Stunden am Rückfluß gekocht. Die wässerige Phase wird zweimal mit Toluol extrahiert und mit der org. Phase vereinigt. Nach üblicher wässeriger Aufarbeitung und chromatographischer Aufreinigung des Rückstandes erhält man 4-[2-(p-Ethoxyphenyl)-ethyl]-2,6-difluor-4'-difluormethylbiphenyl. A mixture of 9.2 g of 2,6-difluoro-4-2- (p-ethoxyphenyl) ethyl phenylboronic acid (Made by reacting 3,5-difluorobenzaldehyde with p-ethoxybenzyltriphenylphosphonium iodide after Wittig and subsequent hydrogenation of the obtained Styrene derivatives on Pd / C), 6.5 g of 1-bromo-4-difluoromethylbenzene, 38 ml 2 M aqueous Na2CO3 solution, 0.6 g tetrakis (triphenylphosphine) palladium- (0) and 75 ml of toluene refluxed for two hours. The aqueous phase will extracted twice with toluene and with the org. Phase united. After the usual aqueous work-up and chromatographic Purification of the residue gives 4- [2- (p-ethoxyphenyl) ethyl] -2,6-difluoro-4'-difluoromethylbiphenyl.

    Beispiele 2 bis 22Examples 2 to 22

    Analog erhält man aus den entsprechenden Vorstufen der Formel II die folgenden erfindungsgemäßen Verbindungen:

    Figure 00370001
    Figure 00380001
    The following compounds according to the invention are obtained analogously from the corresponding precursors of formula II:
    Figure 00370001
    Figure 00380001

    Beispiel 23Example 23

    In einen 800-ml-Hastelloy-Autoklaven, der eine Mischung aus 48 g p-(trans-4-n-Propylcyclohexyl)benzaldehyd und 0,1 g Kaliumfluorid enthält, werden unter Kühlung mit einer Aceton-Trockeneis-Mischung 200 g Schwefeltetrafluorid einkondensiert. Anschließend wird der Autoklav 120 h auf 150° erhitzt. Nach Abkühlen auf ca. 30° wird der gasförmige Inhalt des Autoklaven in Waschflaschen mit Natronlauge abgeleitet. Zum Rückstand werden (unter Rühren) nochmals 5 g Kaliumfluorid, danach 50 ml Pentan, dann unter Eiskühlung 10 g Natriumhydrogencarbonat und schließlich 100 ml Wasser zugegeben. Die organische Phase wird abgetrennt, mit wenig wässriger NaHCO3-Lösung und mit Wasser gewaschen. Nach Abziehen der flüchtigen Bestandteile wird im Hochvakuum (0,1 Torr) bei ca. 180° destilliert. Man erhält p-(trans-4-n-propylcyclohexyl)-difluormethylbenzol, K 14,0 I, 3,7.200 g of sulfuric tetrafluoride are condensed into an 800 ml Hastelloy autoclave which contains a mixture of 48 g of p- (trans-4-n-propylcyclohexyl) benzaldehyde and 0.1 g of potassium fluoride with cooling using an acetone / dry ice mixture . The autoclave is then heated to 150 ° for 120 h. After cooling to approx. 30 °, the gaseous content of the autoclave is drained into wash bottles with sodium hydroxide solution. Another 5 g of potassium fluoride, then 50 ml of pentane, then 10 g of sodium hydrogen carbonate and finally 100 ml of water are added to the residue (with stirring). The organic phase is separated off, washed with a little aqueous NaHCO 3 solution and with water. After the volatile constituents have been stripped off, the mixture is distilled under high vacuum (0.1 Torr) at about 180 °. This gives p- (trans-4-n-propylcyclohexyl) difluoromethylbenzene, K 14.0 I, 3.7.

    Analog werden hergestellt:

  • p-(trans-4-n-pentylcyclohexyl)-difluormethylbenzol
  • p-trans-3-(trans-4-ethylcyclohexyl)-cyclohexyl-difluormethylbenzol
  • p-trans-3-(trans-4-propylcyclohexyl)-cyclohexyl-difluormethylbenzol
  • p-trans-3-(trans-4-butylcyclohexyl)-cyclohexyl-difluormethylbenzol
  • p-trans-3-(trans-4-pentylcyclohexyl)-cyclohexyl-difluormethylbenzol,
  • K 54,0 SB 101,0 N 157,6 I, Δε = +3,2
  • p-trans-3-(trans-4-heptylcyclohexyl)-cyclohexyl-difluormethylbenzol
  • p-[trans-3-(trans-4-ethylcyclohexyl)-cyclohexyl]-o-fluordifluormethylbenzol
  • p-[trans-3-(trans-4-propylcyclohexyl)-cyclohexyl]-o-fluordifluormethylbenzol
  • p-[trans-3-(trans-4-butylcyclohexyl)-cyclohexyl]-o-fluordifluormethylbenzol
  • p-[trans-3-(trans-4-pentylcyclohexyl)-cyclohexyl]-o-fluordifluormethylbenzol
  • 4'-(trans-4-ethylcyclohexyl)-4-difluormethylbiphenyl
  • 4'-(trans-4-propylcyclohexyl)-4-difluormethylbiphenyl
  • 4'-(trans-4-butylcyclohexyl)-4-difluormethylbiphenyl
  • 4'-(trans-4-pentylcyclohexyl)-4-difluormethylbiphenyl,
  • K 122 N 161,8 I, Δε = +4,4
  • 4'-(trans-4-hexylcyclohexyl)-4-difluormethylbiphenyl
  • 4'-(trans-4-heptylcyclohexyl)-4-difluormethylbiphenyl
  • 4'-Ethyl-4'-difluormethylbiphenyl
  • 4'-Propyl-4'-difluormethylbiphenyl
  • 4'-Butyl-4'-difluormethylbiphenyl
  • 4'-Pentyl-4'-difluormethylbiphenyl, K 79 I, Δε = +4,3
  • 4'-Hexyl-4'-difluormethylbiphenyl
  • 4'-Ethoxy-4'-difluormethylbiphenyl
  • 4'-Propoxy-4'-difluormethylbiphenyl
  • 4'-Butoxy-4'-difluormethylbiphenyl
  • 4'-Pentoxy-4'-difluormethylbiphenyl
  • 4'-Hexoxy-4'-difluormethylbiphenyl
    • The following are produced analogously:
  • p- (trans-4-n-pentylcyclohexyl) difluoromethylbenzene
  • p-trans-3- (trans-4-ethylcyclohexyl) cyclohexyl difluoromethylbenzene
  • p-trans-3- (trans-4-propylcyclohexyl) cyclohexyl difluoromethylbenzene
  • p-trans-3- (trans-4-butylcyclohexyl) cyclohexyl difluoromethylbenzene
  • p-trans-3- (trans-4-pentylcyclohexyl) cyclohexyl difluoromethylbenzene,
  • K 54.0 S B 101.0 N 157.6 I, Δε = +3.2
  • p-trans-3- (trans-4-heptylcyclohexyl) cyclohexyl difluoromethylbenzene
  • p- [trans-3- (trans-4-ethylcyclohexyl) cyclohexyl] o-fluorodifluoromethylbenzene
  • p- [trans-3- (trans-4-propylcyclohexyl) cyclohexyl] o-fluorodifluoromethylbenzene
  • p- [trans-3- (trans-4-butylcyclohexyl) cyclohexyl] o-fluorodifluoromethylbenzene
  • p- [trans-3- (trans-4-pentylcyclohexyl) cyclohexyl] o-fluorodifluoromethylbenzene
  • 4 '- (trans-4-ethylcyclohexyl) -4-difluoromethylbiphenyl
  • 4 '- (trans-4-propylcyclohexyl) -4-difluoromethylbiphenyl
  • 4 '- (trans-4-butylcyclohexyl) -4-difluoromethylbiphenyl
  • 4 '- (trans-4-pentylcyclohexyl) -4-difluoromethylbiphenyl,
  • K 122 N 161.8 I, Δε = +4.4
  • 4 '- (trans-4-hexylcyclohexyl) -4-difluoromethylbiphenyl
  • 4 '- (trans-4-heptylcyclohexyl) -4-difluoromethylbiphenyl
  • 4'-ethyl-4'-difluoromethylbiphenyl
  • 4'-propyl-4'-difluoromethylbiphenyl
  • 4'-butyl-4'-difluoromethylbiphenyl
  • 4'-pentyl-4'-difluoromethylbiphenyl, K 79 I, Δε = +4.3
  • 4'-hexyl-4'-difluoromethylbiphenyl
  • 4'-ethoxy-4'-difluoromethylbiphenyl
  • 4'-propoxy-4'-difluoromethylbiphenyl
  • 4'-butoxy-4'-difluoromethylbiphenyl
  • 4'-pentoxy-4'-difluoromethylbiphenyl
  • 4'-hexoxy-4'-difluoromethylbiphenyl

    • Beispiel 24Example 24 4-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-2,6-difluor-difluormethylbenzol4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2,6-difluoro-difluoromethylbenzene

  • a) 4-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-2,6-difluorjodbenzola) 4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2,6-difluoroiodobenzene
  • Zu einer Mischung von 0,094 mol 3-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-1,5-difluorbenzol, 15 ml TMEDA und 300 ml THF wird bei -65 °C 62 ml einer Lösung von n-Butyllithium (15%ig) in Hexan getropft. Anschließend wird bei -60 °C eine Lösung von 0,094 mol Jod in 50 ml THF zugegeben. Nach Zugabe von 60 ml Wasser und 30 ml einer gesättigten Natriumhydrogensulfitlösung wird die wäßrige Phase abgetrennt, die organische Phase wird mit einer gesättigten Kochsalz-Lösung gewaschen, getrocknet über Magnesiumsulfat und im Vakuum eingeengt. Der Rückstand wird aus 200 ml Ethanol umkristallisiert. To a mixture of 0.094 mol of 3- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1,5-difluorobenzene, 15 ml TMEDA and 300 ml THF becomes 62 ml of a solution at -65 ° C of n-butyllithium (15%) dropped in hexane. Subsequently is a solution of 0.094 mol iodine in at -60 ° C. 50 ml THF added. After adding 60 ml of water and 30 ml of a saturated Sodium hydrogen sulfite solution becomes the aqueous phase separated, the organic phase is saturated Washed saline solution, dried over Magnesium sulfate and concentrated in vacuo. The residue is recrystallized from 200 ml of ethanol.
  • b) 4-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-2,6-difluorbenzaldehyd Ein Gemisch aus 0,0224 mol 25a und 50 ml THF wird bei -70 °C mit 14 ml einer 15%igen Lösung von n-Butyllithium in Hexan versetzt. Nach 1stündigem Rühren bei -70 °C wird ein Gemisch aus 0,0224 mol N-Formylpiperidin und 20 ml THF hinzugetropft. Nach Aufwärmen auf -5 °C wird Wasser hinzugegeben.Die wäßrige Phase wird abgetrennt, die organische Phase wird mit Wasser und einer gesättigten Bicarbonat-Lösung gewaschen, über Natriumsulfat getrocknet, filtriert und eingeengt. Der Rückstand wird mit Hexan als Laufmittel über eine mit Kieselgel gefüllte Säule chromatographiert, und anschließend aus Hexan umkristallisiert.b) 4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2,6-difluorobenzaldehyde A mixture of 0.0224 mol 25a and 50 ml THF is mixed with 14 ml of a 15% solution at -70 ° C Solution of n-butyllithium in hexane added. After stirring for 1 hour at -70 ° C., a mixture of 0.0224 mol of N-formylpiperidine and 20 ml of THF is added dropwise. After warming to -5 ° C., water is added. The aqueous phase is separated off, the organic phase is washed with water and a saturated bicarbonate solution, dried over sodium sulfate, filtered and concentrated. The residue is chromatographed with hexane as the eluent on a column filled with silica gel, and then recrystallized from hexane.
  • c) 4-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-2,6-difluor-1-difluormethylbenzol Zu einem Gemisch aus 0,02 mol Diethylaminoschwefeltrifluorid (DAST) und 5 ml Dichlormethan werden bei Raumtemperatur 0,01 mol 25b gegeben und 2 Stunden zum Sieden erhitzt. Nach zweistündigem Erhitzen werden nochmals 0,01 mol DAST hinzugesetzt und weitere 3 Stunden erhitzt. Nach Abkühlen auf 0 °C werden 25 ml Wasser hinzugesetzt. Nach Abtrennen der wäßrigen Phase wird die organische Phase mit Wasser gewaschen, über Natriumsulfat getrocknet, filtriert und im Vakuum eingeengt. Der Rückstand wird mit Petrolether über eine mit Kieselgel gefüllte Säule chromatograhiert und aus Isopropanol umkristallisiert. Das Produkt zeigt: K 92 N 99,2 I, Δε = +8,99.c) 4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2,6-difluoro-1-difluoromethylbenzene At room temperature, 0. 01 mol 25b added and heated to boiling for 2 hours. After heating for two hours, a further 0.01 mol of DAST are added and the mixture is heated for a further 3 hours. After cooling to 0 ° C, 25 ml of water are added. After the aqueous phase has been separated off, the organic phase is washed with water, dried over sodium sulfate, filtered and concentrated in vacuo. The residue is chromatographed with petroleum ether on a column filled with silica gel and recrystallized from isopropanol. The product shows: K 92 N 99.2 I, Δε = +8.99.

    • Beispiele 25 bis 37Examples 25 to 37

    Analog erhält man aus den entsprechenden Vorstufen die folgenden Verbindungen der Formel Ia

    Figure 00430001
    Figure 00440001
    The following compounds of the formula Ia are obtained analogously from the corresponding precursors
    Figure 00430001
    Figure 00440001

    Beispiel AExample A

    Zu einem flüssigkristallinen Medium A bestehend aus

    22 %
    p-(trans-4-Propylcyclohexyl)-ethylbenzol
    20 %
    p-(trans-4-Propylcyclohexyl)-methoxybenzol
    15 %
    p-(trans-4-Propylcyclohexyl)-ethoxybenzol
    19 %
    4-p-(trans-4-Propylcyclohexyl)-4'-ethylbiphenyl
    14 %
    4-p-(trans-4-Pentylcyclohexyl)-4'-ethylbiphenyl
    5 %
    4,4'-Bis-(trans-4-Propylcyclohexyl)-biphenyl
    5 %
    4-(trans-4-Propylcyclohexyl)-4'-(trans-4-pentylcyclohexyl)-biphenyl
    werden jeweils 10 % einer der folgenden erfindungsgemäßen Verbindungen zugegeben:
    A1
    p-(trans-4-Propylcyclohexyl)-difluormethylbenzol
    A2
    p-[trans-4-(trans-4-Pentylcyclohexyl)-cyclohexyl]-difluormethylbenzol
    A3
    4-(trans-4-Propylcyclohexyl)-4'-difluormethylbiphenyl
    To a liquid crystalline medium A consisting of
    22%
    p- (trans-4-propylcyclohexyl) ethylbenzene
    20%
    p- (trans-4-propylcyclohexyl) methoxybenzene
    15%
    p- (trans-4-propylcyclohexyl) ethoxybenzene
    19%
    4-p- (trans-4-propylcyclohexyl) -4'-ethylbiphenyl
    14%
    4-p- (trans-4-pentylcyclohexyl) -4'-ethylbiphenyl
    5%
    4,4'-bis (trans-4-propylcyclohexyl) biphenyl
    5%
    4- (trans-4-propylcyclohexyl) -4 '- (trans-4-pentylcyclohexyl) biphenyl
    10% each of the following compounds according to the invention are added:
    A1
    p- (trans-4-propylcyclohexyl) difluoromethylbenzene
    A2
    p- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] difluoromethylbenzene
    A3
    4- (trans-4-propylcyclohexyl) -4'-difluoromethylbiphenyl

    Die physikalischen Eigenschaften der so hergestellten flüssigkristallinen Medien können der Tabelle I entnommen werden: Medium Phasenübergang Δε Δn Viskosität m2s-1 (20 °C) A s < -20 N 72 I 0,06 0,1131 11 A1 S < -20 N 59, SI 0,43 0,1052 11,4 A2 S < -20 N 79,9 I 0,38 0,1122 12,7 A3 S < +10 N 81,6 I 0,50 0,1190 13,12 The physical properties of the liquid-crystalline media prepared in this way can be found in Table I: medium Phase transition Δε Δn Viscosity m 2 s -1 (20 ° C) A s <-20 N 72 I 0.06 0.1311 11 A1 S <-20 N 59, SI 0.43 0.1052 11.4 A2 S <-20 N 79.9 I 0.38 0.1122 12.7 A3 S <+10 N 81.6 I 0.50 0.1190 13.12

    Beispiel BExample B

    Man stellt ein flüssigkristallines Medium her bestehend aus

    9,0 %
    p-(trans-4-Pentylcyclohexyl)-fluorbenzol
    7,2 %
    p-(trans-4-Hexylcyclohexyl)-fluorbenzol
    5,4 %
    p-(trans-4-Heptylcyclohexyl)-fluorbenzol
    7,2 %
    p-[trans-4-(trans-4-Ethylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    10,8 %
    p-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    8,1 %
    p-[trans-4-(trans-4-Butylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    8,1 %
    p-[trans-4-(trans-4-Pentylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    10,8 %
    4'-(trans-4-Propylcyclohexyl)-3,4-difluorbiphenyl
    9,0 %
    4'-(trans-4-Pentylcyclohexyl)-3,4-difluorbiphenyl
    4,5 %
    2-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-1-(4-trifluormethoxyphenyl)-ethan
    4,5 %
    2-[trans-4-(trans-4-Pentylcyclohexyl)-cyclohexyl]-1-(4-trifluormethoxyphenyl)-ethan
    1,8 %
    4,4'-Bis-(trans-4-Propylcyclohexyl)-2-fluorbiphenyl
    1,8 %
    4,4'-Bis-(trans-4-Pentylcyclohexyl)-2-fluorbiphenyl
    1,8 %
    4-(trans-4-Propylcyclohexyl)-4'-(trans-4-pentylcyclohexyl)-2'-fluorbiphenyl
    10,0 %
    4-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-2,6-difluor-1-difluormethylbenzol
    A liquid-crystalline medium is made up of
    9.0%
    p- (trans-4-pentylcyclohexyl) fluorobenzene
    7.2%
    p- (trans-4-hexylcyclohexyl) fluorobenzene
    5.4%
    p- (trans-4-heptylcyclohexyl) fluorobenzene
    7.2%
    p- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    10.8%
    p- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    8.1%
    p- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    8.1%
    p- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    10.8%
    4 '- (trans-4-propylcyclohexyl) -3,4-difluorobiphenyl
    9.0%
    4 '- (trans-4-pentylcyclohexyl) -3,4-difluorobiphenyl
    4.5%
    2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1- (4-trifluoromethoxyphenyl) ethane
    4.5%
    2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] -1- (4-trifluoromethoxyphenyl) ethane
    1.8%
    4,4'-bis (trans-4-propylcyclohexyl) -2-fluorobiphenyl
    1.8%
    4,4'-bis (trans-4-pentylcyclohexyl) -2-fluorobiphenyl
    1.8%
    4- (trans-4-propylcyclohexyl) -4 '- (trans-4-pentylcyclohexyl) -2'-fluorobiphenyl
    10.0%
    4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2,6-difluoro-1-difluoromethylbenzene

    Dieses Medium weist folgende physikalische Eigenschaften auf:

  • S < -20 N 89,7 I, Δε 5,58, Δn 0,0954, Viskosität (20 °C): 16,8 mm2s-1
    • This medium has the following physical properties:
  • S <-20 N 89.7 I, Δε 5.58, Δn 0.0954, viscosity (20 ° C): 16.8 mm 2 s -1

    • Beispiel CExample C

    Man stellt ein flüssigkristallines Medium her bestehend aus

    7,0 %
    p-(trans-4-Pentylcyclohexyl)-fluorbenzol
    8,0 %
    p-(trans-4-Hexylcyclohexyl)-fluorbenzol
    6,0 %
    p-(trans-4-Heptylcyclohexyl)-fluorbenzol
    8,0 %
    p-(trans-4-Pentylcyclohexyl)-difluormethylbenzol
    5,0 %
    p-[trans-4-(trans-4-Ethylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    6,0 %
    p[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    6,0 %
    p-[trans-4-(trans-4-Butylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    6,0 %
    p-[trans-4-(trans-4-Pentylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    9,0 %
    p-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-di fluormethylbenzol
    9,0 %
    p-[trans-4-(trans-4-Pentylcyclohexyl)-cyclohexyl]-difluormethylbenzol
    8,0 %
    4'-(trans-4-Pentylcyclohexyl)-4-difluormethylbiphenyl
    8,0 %
    4'-(trans-4-Pentylcyclohexyl)-4-(difluorchlormethyl)-3,5-difluorbiphenyl
    6,0 %
    4'-(trans-4-Pentylcyclohexyl)-4-difluormethyl-3,5-difluorbiphenyl
    3,0 %
    4,4'-Bis-(trans-4-pentylcyclohexyl)-2-fluorbiphenyl
    4,0 %
    4,4'-Bis-(trans-4-propylcyclohexyl)-2-fluorbiphenyl
    3,0 %
    4-(trans-4-Propylcyclohexyl)-4'-(trans-4-pentylcyclohexyl)-2'-fluorbiphenyl
    A liquid-crystalline medium is made up of
    7.0%
    p- (trans-4-pentylcyclohexyl) fluorobenzene
    8.0%
    p- (trans-4-hexylcyclohexyl) fluorobenzene
    6.0%
    p- (trans-4-heptylcyclohexyl) fluorobenzene
    8.0%
    p- (trans-4-pentylcyclohexyl) difluoromethylbenzene
    5.0%
    p- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    6.0%
    p [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    6.0%
    p- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    6.0%
    p- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    9.0%
    p- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] di fluoromethylbenzene
    9.0%
    p- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] difluoromethylbenzene
    8.0%
    4 '- (trans-4-pentylcyclohexyl) -4-difluoromethylbiphenyl
    8.0%
    4 '- (trans-4-pentylcyclohexyl) -4- (difluorochloromethyl) -3,5-difluorobiphenyl
    6.0%
    4 '- (trans-4-pentylcyclohexyl) -4-difluoromethyl-3,5-difluorobiphenyl
    3.0%
    4,4'-bis (trans-4-pentylcyclohexyl) -2-fluorobiphenyl
    4.0%
    4,4'-bis (trans-4-propylcyclohexyl) -2-fluorobiphenyl
    3.0%
    4- (trans-4-propylcyclohexyl) -4 '- (trans-4-pentylcyclohexyl) -2'-fluorobiphenyl

    Beispiel DExample D

    Man stellt ein flüssigkristallines Medium her bestehend aus

    7,0 %
    p-(trans-4-Pentylcyclohexyl)-fluorbenzol
    6,0 %
    p-(trans-4-Hexylcyclohexyl)-fluorbenzol
    6,0 %
    p-(trans-4-Heptylcyclohexyl)-fluorbenzol
    8,0 %
    p-(trans-4-Pentylcyclohexyl)-difluormethylbenzol
    5,0 %
    p-[trans-4-(trans-4-Ethylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    6,0 %
    p-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    6,0 %
    p-[trans-4-(trans-4-Butylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    6,0 %
    p-[trans-4-(trans-4-Pentylcyclohexyl)-cyclohexyl]-trifluormethoxybenzol
    9,0 %
    p-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-difluormethyl-2,6-difluorbenzol
    9,0 %
    p-[trans-4-(trans-4-Pentylcyclohexyl)-cyclohexyl]-difluormethylbenzol
    4,0 %
    4'-(trans-4-Pentylcyclohexyl)-3,4-difluorbiphenyl
    8,0 %
    4'-(trans-4-Propylcyclohexyl)-3,4-difluorbiphenyl
    5,0 %
    1-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-2-(trifluormethoxyphenyl)-ethan
    5,0 %
    1-[trans-4-(trans-4-Propylcyclohexyl)-cyclohexyl]-2-(trifluormethoxyphenyl)-ethan
    3,0 %
    4,4'-Bis-(trans-4-pentylcyclohexyl)-2-fluorbiphenyl
    4,0 %
    4,4'-Bis-(trans-4-propylcyclohexyl)-2-fluorbiphenyl
    3,0 %
    4-(trans-4-Propylcyclohexyl)-4'-(trans-4-pentylcyclohexyl)-2'-fluorbiphenyl
    A liquid-crystalline medium is made up of
    7.0%
    p- (trans-4-pentylcyclohexyl) fluorobenzene
    6.0%
    p- (trans-4-hexylcyclohexyl) fluorobenzene
    6.0%
    p- (trans-4-heptylcyclohexyl) fluorobenzene
    8.0%
    p- (trans-4-pentylcyclohexyl) difluoromethylbenzene
    5.0%
    p- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    6.0%
    p- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    6.0%
    p- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    6.0%
    p- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] trifluoromethoxybenzene
    9.0%
    p- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] difluoromethyl-2,6-difluorobenzene
    9.0%
    p- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] difluoromethylbenzene
    4.0%
    4 '- (trans-4-pentylcyclohexyl) -3,4-difluorobiphenyl
    8.0%
    4 '- (trans-4-propylcyclohexyl) -3,4-difluorobiphenyl
    5.0%
    1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2- (trifluoromethoxyphenyl) ethane
    5.0%
    1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2- (trifluoromethoxyphenyl) ethane
    3.0%
    4,4'-bis (trans-4-pentylcyclohexyl) -2-fluorobiphenyl
    4.0%
    4,4'-bis (trans-4-propylcyclohexyl) -2-fluorobiphenyl
    3.0%
    4- (trans-4-propylcyclohexyl) -4 '- (trans-4-pentylcyclohexyl) -2'-fluorobiphenyl

    Claims (7)

    1. Difluoromethyl compounds of the formula I
      Figure 00590001
      where
      R
      is an alkyl or alkenyl radical having 1 to 15 carbon atoms which is unsubstituted or at least monosubstituted by halogen, it also being possible for one or more CH2 groups in this radical to be replaced, in each case independently of one another, by -O-, -S-,
      Figure 00590002
      -CO-, -CO-O-, -O-CO- or -O-CO-O- in such a manner that oxygen atoms are not linked directly to one another,
      A1
      is
      • (a) a trans-1,4-cyclohexylene radical in which, in addition, one or more non-adjacent CH2 groups may be replaced by -O- and/or -S-,
      • (b) a 1,4-phenylene ring in which, in addition, one or two CH groups may be replaced by N,
      • (c) a radical from the group comprising 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
        it being possible for the radicals (a) and (b) to be substituted by CN or monosubstituted or disubstituted by fluorine,
      L1 and L2
      in each case independently of one another, are H or F,
      Z1
      is -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH2CH2-, -CH=CH-, -C≡C- or a single bond,
      m
      is 1, 2 or 3,
    2. Difluoromethyl compounds according to Claim 1, of formula IA
      Figure 00600001
      where R, A1, Z1 and m are as defined above.
    3. Difluoromethyl compounds according to Claim 2, of the formula IA'
      Figure 00600002
      where R is as defined above,
      m
      is 0 or 1,
      Figure 00600003
      and
      o
      is 0 or 1.
    4. Use of compounds of the formula I as components of liquid-crystalline media.
    5. Liquid-crystalline medium having at least two liquid-crystalline components, characterised in that it contains at least one compound of the formula I.
    6. Liquid-crystal display, characterised in that it contains a liquid-crystalline medium according to Claim 3.
    7. Electrooptical display, characterised in that it contains, as dielectric, a liquid-crystalline medium according to Claim 3.
    EP91103627A 1990-03-24 1991-03-09 Difluoromethyl compounds and liquid criystal medium Expired - Lifetime EP0449015B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE4009564 1990-03-24
    DE4009564 1990-03-24

    Publications (3)

    Publication Number Publication Date
    EP0449015A2 EP0449015A2 (en) 1991-10-02
    EP0449015A3 EP0449015A3 (en) 1991-11-06
    EP0449015B1 true EP0449015B1 (en) 1998-07-01

    Family

    ID=6403021

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP91103627A Expired - Lifetime EP0449015B1 (en) 1990-03-24 1991-03-09 Difluoromethyl compounds and liquid criystal medium

    Country Status (3)

    Country Link
    EP (1) EP0449015B1 (en)
    JP (1) JP2959590B2 (en)
    DE (1) DE59109017D1 (en)

    Families Citing this family (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE59108172D1 (en) * 1990-04-13 1996-10-17 Merck Patent Gmbh LIQUID CRYSTAL MEDIUM
    DE4239169A1 (en) * 1992-11-21 1994-05-26 Merck Patent Gmbh Cyclobutane - benzene derivatives
    DE4423098A1 (en) 1994-07-01 1996-01-04 Hoechst Ag Use of conjugated compounds containing pyrimidine groups as electroluminescent materials
    DE19528085A1 (en) * 1994-08-06 1996-02-08 Merck Patent Gmbh Liquid crystal medium for electro-optical displays
    DE4445224B4 (en) * 1994-12-17 2014-03-27 Merck Patent Gmbh benzene derivatives
    JP4044618B2 (en) 1996-11-28 2008-02-06 チッソ株式会社 Fluorine-substituted benzene derivative, liquid crystal composition, and liquid crystal display device
    JP4288729B2 (en) * 1998-09-28 2009-07-01 チッソ株式会社 Benzene derivative and method for producing the same
    DE19858856A1 (en) * 1998-12-19 2000-06-21 Merck Patent Gmbh Process for the preparation of aryl metal compounds and their reaction with electrophiles

    Citations (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0255236A2 (en) * 1986-06-30 1988-02-03 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
    WO1989002884A1 (en) * 1987-09-25 1989-04-06 MERCK Patent Gesellschaft mit beschränkter Haftung Substituted phenyltrifluormethylethers

    Family Cites Families (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE3614778A1 (en) * 1986-05-02 1987-11-05 Merck Patent Gmbh Smectic liquid crystal phases
    DE3909802A1 (en) * 1988-07-27 1990-04-05 Merck Patent Gmbh DIFLUORMETHYLVERBINDUNGEN
    DE3904817A1 (en) * 1989-02-17 1990-09-20 Nematel Dr Rudolf Eidenschink Difluoromethyl compounds
    EP0628532B1 (en) * 1989-09-06 2000-01-19 MERCK PATENT GmbH Fluorobenzole derivatives and mesomorphous medium

    Patent Citations (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0255236A2 (en) * 1986-06-30 1988-02-03 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
    WO1989002884A1 (en) * 1987-09-25 1989-04-06 MERCK Patent Gesellschaft mit beschränkter Haftung Substituted phenyltrifluormethylethers

    Also Published As

    Publication number Publication date
    EP0449015A2 (en) 1991-10-02
    JP2959590B2 (en) 1999-10-06
    DE59109017D1 (en) 1998-08-06
    EP0449015A3 (en) 1991-11-06
    JPH04217930A (en) 1992-08-07

    Similar Documents

    Publication Publication Date Title
    EP0628532B1 (en) Fluorobenzole derivatives and mesomorphous medium
    EP0541793B1 (en) Vinyl compounds and liquid-crystal medium
    EP0462237B1 (en) 1,2-disubstituted 2,6-difluorobenzene compounds and liquid crystal media
    DE19513007A1 (en) Fluoro-phenyl hexa:fluoro-propyl ethers useful in liquid crystal media
    DE4142519B4 (en) Fluorobenzene derivatives
    EP0525140B1 (en) Liquid-crystal compounds
    WO1994021747A1 (en) 1,2,2,2-tetrafluoroethylethers and liquid crystal medium
    DE4215277B4 (en) Benzene derivatives and their use for a liquid crystalline medium
    EP0449015B1 (en) Difluoromethyl compounds and liquid criystal medium
    DE4416256B4 (en) Partially fluorinated benzene derivatives and liquid crystalline medium
    DE4137401C2 (en) Benzene derivatives and liquid crystalline medium
    WO1994026839A1 (en) Partially fluorinated benzene derivatives
    EP1515931B1 (en) 3,3,4,4-tetrafluorocyclopentane compounds, used as components of liquid crystal media
    EP0721933B1 (en) 1,4-Disubstituted 2,6-difluorobenzene compounds and liquid crystal media
    WO1993003113A1 (en) Liquid-crystal compounds
    DE19607996B4 (en) Liquid-crystalline medium containing at least one substituted cyclohex-3-en-yl derivative
    DE4111991B4 (en) 1,4-Disubstituted 2,6-difluorobenzene compounds and their uses
    DE19607999A1 (en) Stable liquid crystalline or mesogenic substituted cyclopentenyl derivatives
    DE4425642A1 (en) Stable liquid crystalline or mesogenic substd. benzyl fluoro-alkyl ether(s)
    DE19504518A1 (en) Partially fluorinated benzene derivs. useful in liq. crystalline media
    DE4000534C2 (en) 1,4-disubstituted 2,6-difluorobenzene compounds and liquid-crystalline medium
    DE19902616B4 (en) Tetrahydrofuranocyclohexan derivatives
    DE4107641A1 (en) New di:fluoro-methyl substd. cyclic cpds. used in liq. crystal medium
    DE4030031A1 (en) New substd. methoxyethyl-benzene derivs. - useful as components of liq. crystal media
    DE19958154A1 (en) New partly fluorinated 4-(cyanotetrafluorosulfanyl)-phenyl or benzoate derivatives of (hetero)cyclic compounds useful in liquid media for displays and new 4-(cyanotetrafluorosulfanyl)-benzene derivatives

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): DE GB

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): DE GB

    17P Request for examination filed

    Effective date: 19920408

    17Q First examination report despatched

    Effective date: 19941012

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): DE GB

    REF Corresponds to:

    Ref document number: 59109017

    Country of ref document: DE

    Date of ref document: 19980806

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 19980924

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 19990311

    Year of fee payment: 9

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed
    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20000309

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20000309

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20060302

    Year of fee payment: 16

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20071002